CN113540475A - Method for improving activity of noble metal catalyst - Google Patents
Method for improving activity of noble metal catalyst Download PDFInfo
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- CN113540475A CN113540475A CN202110782656.3A CN202110782656A CN113540475A CN 113540475 A CN113540475 A CN 113540475A CN 202110782656 A CN202110782656 A CN 202110782656A CN 113540475 A CN113540475 A CN 113540475A
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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
- H01M4/8882—Heat treatment, e.g. drying, baking
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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
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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
- H01M4/928—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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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 method for improving the activity of a noble metal catalyst, which comprises the following steps: step S1, dipping a noble metal catalyst in a metal salt solution, and heating the solution; adding a metal contained in the metal salt solution to the noble metal catalyst by a reaction; and step S2, carrying out solid-liquid separation, washing the filter residue with water, and drying to obtain a post-treatment product. The noble metal catalyst is a platinum alloy catalyst and comprises platinum metal and another more active metal which is more active than the platinum metal; the metal salt solution can react with the more active metal to displace the more active metal, and the metal contained in the metal salt solution is added to the platinum alloy catalyst in the reaction process. The method can realize the conversion from the binary metal catalyst to the ternary or even multi-element metal catalyst, and can increase and regulate the content of a certain element in the catalyst, thereby improving the activity of the catalyst.
Description
Technical Field
The invention belongs to the field of new energy materials and application, and particularly relates to a method for improving the activity of a noble metal catalyst.
Background
Proton exchange membrane fuel cells are an important form of utilization of hydrogen energy. The catalyst is the core component of the proton exchange membrane fuel cell, and the quality of the performance of the catalyst directly determines the quality of the membrane electrode performance. At this stage, platinum is still the best proton exchange membrane fuel cell catalyst. However, the existing platinum-based catalyst has the defect of low catalyst activity, in order to improve the platinum utilization rate, the catalyst is generally subjected to carrier pretreatment, catalyst hydrophilic and hydrophobic post-treatment and other operations, and a carbon material with a special structure is also selected as a carrier. The electrochemical performance of the platinum-based catalyst is improved by a simple dipping, heating and stirring method.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method which is simple and easy to operate, is more environment-friendly and improves the electrochemical activity of a platinum-based catalyst. In order to achieve the technical purpose, the embodiment of the invention adopts the technical scheme that:
the embodiment of the invention provides a method for improving the activity of a noble metal catalyst, which comprises the following steps:
step S1, dipping a noble metal catalyst in a metal salt solution, and heating the solution; adding a metal contained in the metal salt solution to the noble metal catalyst by a reaction;
and step S2, carrying out solid-liquid separation, washing the filter residue with water, and drying to obtain a post-treatment product.
Specifically, the noble metal catalyst is a platinum alloy catalyst comprising platinum metal and another more active metal that is more active than the platinum metal;
the metal salt solution can react with the more active metal to displace the more active metal, and the metal contained in the metal salt solution is added to the platinum alloy catalyst in the reaction process.
Preferably, the more active metal in the platinum alloy catalyst is selected from one of cobalt, nickel, copper, manganese, zinc, magnesium and aluminum.
Preferably, the metal salt solution is selected from one or more of cobalt salt, nickel salt, copper salt, manganese salt, zinc salt, magnesium salt, aluminum salt and platinum salt.
Preferably, the molar ratio of the metal ions in the metal salt solution to the more active metal atoms in the platinum alloy catalyst is 0.1-13.7.
Preferably, the molar ratio of the metal ions in the metal salt solution to the more active metal atoms in the platinum alloy catalyst is 5-9.
Preferably, in step S1, the heating treatment is performed by a water bath, an oil bath, or a metal bath; the heating temperature is 50-90 ℃; the heating time is 0.5-6 h.
Preferably, in step S1, the heating temperature is 70-90 ℃ and the heating time is 2-3 h.
Preferably, the drying temperature in step S2 is 50 to 120 ℃.
Preferably, the concentration of the metal salt solution is 0.01-3.00 mol/L.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
1) the method can introduce other metal elements into the noble metal catalyst by dipping the noble metal catalyst into a metal salt solution and carrying out heat treatment, thereby realizing the conversion of a binary metal catalyst into a ternary or even a multi-element metal catalyst, increasing and regulating the content of a certain element in the catalyst, and further improving the activity of the catalyst;
2) the method only needs simple heating and stirring, does not need operating conditions such as high temperature, high pressure and the like, and has mild reaction, safety, simplicity and easy operation;
3) the method mainly adopts water as a solvent, and is more environment-friendly.
Drawings
FIG. 1 is an XRD pattern of the catalyst before and after treatment in example 2 of the present invention.
FIG. 2 is a LSV curve for the catalyst before and after treatment in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a method for improving the activity of a noble metal catalyst, which comprises the following steps:
step S1, dipping a noble metal catalyst in a metal salt solution, and heating the solution; adding a metal contained in the metal salt solution to the noble metal catalyst by a reaction;
and step S2, carrying out solid-liquid separation, washing the filter residue with water, and drying to obtain a post-treatment product.
According to the method provided by the embodiment of the invention, the conversion from a binary metal catalyst to a ternary or even multi-element metal catalyst can be realized by introducing other metal elements, or the content of a certain specific metal element in a noble metal catalyst can be increased; so as to improve the electrochemical activity of the catalyst.
Specifically, the noble metal catalyst is a platinum alloy catalyst comprising platinum metal and another more active metal that is more active than the platinum metal; the metal salt solution can react with the more active metal to displace the more active metal, and the metal contained in the metal salt solution is added to the platinum alloy catalyst in the reaction process.
The platinum alloy catalyst is a core component of the proton exchange membrane fuel cell, the performance of the catalyst directly determines the performance of the membrane electrode, and the transition of the binary platinum alloy catalyst to a ternary or even multi-element metal catalyst can be realized or the platinum metal content in the binary platinum alloy catalyst is improved by the reaction of a metal salt solution and a more active metal in the platinum alloy catalyst;
preferably, the more active metal in the platinum alloy catalyst is selected from one of cobalt, nickel, copper, manganese, zinc, magnesium and aluminum; the metal salt solution is selected from one or more of cobalt salt, nickel salt, copper salt, manganese salt, zinc salt, magnesium salt, aluminum salt and platinum salt;
when a specific metal salt solution is selected, the more active metal component in the platinum alloy catalyst needs to be considered, so that the metal salt solution can react with the more active metal component in the platinum alloy catalyst; for example, when the more active metal in the platinum alloy catalyst is cobalt, the metal salt solution can be copper nitrate solution;
preferably, the molar ratio of the metal ions in the metal salt solution to the more active metal atoms in the platinum alloy catalyst is 0.1 to 13.7, and may be, for example, 0.1, 1.0, 3.0, 5.0, 7.0, 9.0, 11.0, 13.0, 13.7, and the like.
Preferably, the molar ratio of the metal ions in the metal salt solution to the more active metal atoms in the platinum alloy catalyst is 5 to 9, and may be, for example, 5, 6, 7, 8, 9, or the like.
Preferably, in step S1, the heating treatment is performed by a water bath, an oil bath, or a metal bath; the heating temperature is 50 to 90 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and the like; the heating time is 0.5 to 6.0 hours, for example, 0.5 hour, 1.0 hour, 2.0 hours, 3.0 hours, 4.0 hours, 5.0 hours, 6.0 hours, etc.
The reaction can be accelerated by the above-mentioned heat treatment.
Preferably, in step S1, the heating temperature is 70 to 90 ℃, for example, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and the like; the heating time is 2 to 3 hours, for example, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours.
Preferably, in step S2, the drying temperature is 50 to 120 ℃, for example, 50 ℃, 70 ℃, 90 ℃, 110 ℃, 120 ℃ and the like.
Preferably, the concentration of the metal salt solution is 0.01 to 3.00mol/L, and may be, for example, 0.01mol/L, 0.1mol/L, 0.5mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, or the like.
In the following specific examples, those whose operations are not subject to the conditions indicated, were carried out according to the usual conditions or conditions recommended by the manufacturer. All raw materials are conventional products which can be obtained commercially by manufacturers and specifications.
Wherein, isopropanol (analytically pure, not less than 99.7 percent), perchloric acid (superior pure, 70.0-72.0 percent) and cupric nitrate (analytically pure, not less than 99.5 percent) are purchased from national medicine group chemical reagent company Limited, Nafion solution (5 wt percent, model D520) is purchased from western scientific and technical company Limited, and chloroplatinic acid is purchased from Nanjing Yishengli chemical company Limited.
The test apparatus for X-ray powder diffraction (XRD) was a Rigaku MiniFlex 600X-ray diffractometer from Rigaku corporation, Japan. The test conditions were: power: 0.60 kW, 2 θ test range: +2 ° +145 °, θ/2 θ axis minimum step angle: 0.01 ° (2 θ), constant scan speed: 0.01-100 DEG/min, scanning range: 2 θ =30 ° to 90 °, scanning speed: 5 °/min, step size: 0.02 degree.
The test instrument for Linear Sweep Voltammetry (LSV) electrochemical testing was 706E electrochemical workstation of shanghai chenhua instruments ltd. The measurement conditions were: the working electrode has a geometric area of 0.19625cm2The Rotating Disk Electrode (RDE) of (1 mg catalyst/1 mL solvent, 1mL solvent composition comprising: 0.6mL of ultrapure water, 0.4mL of isopropanol, and 0.025mL of Nafion membrane solution, and dispersing the catalyst in the solvent using a cell disruptor, and sonicating for 30min to form a uniformly dispersed ink. The loading capacity of the catalyst on the working electrode is 10 mug/10 mul, 10 mul of catalyst ink is dripped on the working electrode, and the catalyst ink forms a uniform film after being irradiated by an infrared lamp or naturally dried. The testing process comprises the following steps: before testing, oxygen needs to be introduced into the electrolyte for 20min, the oxygen introduction state is continuously kept in the testing process, and the internal resistance of the system is measured to ensure that the internal resistance of the perchloric acid system is less than 30 omega. The working electrode adopts the prepared uniform RDE, the counter electrode adopts a platinum mesh counter electrode with the thickness of 10mm multiplied by 5mm, the reference electrode adopts a mercury-Mercurous Sulfate Electrode (MSE), the scanning potential interval of an electrocatalytic oxygen reduction (ORR) test is-0.513-0.387V, the scanning speed is 10mV/s, and the temperature is 25 ℃.
Example 1
A method of increasing the activity of a noble metal catalyst comprising the steps of:
step 1, designing the molar ratio of copper ions in a metal salt solution to cobalt atoms in a platinum alloy catalyst to be 2. Selecting 1g of platinum-cobalt alloy catalyst with the cobalt content of 10%, dispersing the platinum-cobalt alloy catalyst in 340mL of copper nitrate solution with the concentration of 0.01mol/L, heating in a water bath at 60 ℃ and stirring for 1.5h to obtain a reaction product.
And 2, filtering and washing the reaction product, and drying in a 65-DEG C forced air drying oven for 24h to obtain the platinum-cobalt-copper alloy catalyst with copper added into the platinum-cobalt alloy catalyst.
Example 2
A method of increasing the activity of a noble metal catalyst comprising the steps of:
step 1, designing the molar ratio of copper ions in a metal salt solution to nickel atoms in a platinum alloy catalyst to be 2.3, selecting 1g of the platinum-nickel alloy catalyst, wherein the nickel content is 15%, dispersing the platinum-nickel alloy catalyst in 588mL of copper nitrate solution with the concentration of 0.01mol/L, heating in a water bath at the temperature of 80 ℃, and stirring for 3 hours to obtain a reaction product.
And 2, filtering and washing the reaction product, and drying in a blowing drying oven at 90 ℃ for 24h to obtain the platinum nickel copper alloy catalyst with copper added into the platinum nickel alloy catalyst.
Example 3
A method of increasing the activity of a noble metal catalyst comprising the steps of:
step 1, designing the molar ratio of platinum ions in a metal salt solution to cobalt atoms in a platinum alloy catalyst to be 3, selecting 1g of the platinum-cobalt alloy catalyst, wherein the cobalt content is 10%, dispersing the platinum-cobalt alloy catalyst in 510mL of chloroplatinic acid solution with the concentration of 0.01mol/L, heating in a water bath at 75 ℃, and stirring for 2 hours to obtain a reaction product.
And 2, filtering and washing the reaction product, and drying in a forced air drying oven at 80 ℃ for 24 hours to obtain the platinum-cobalt alloy catalyst with the platinum loading capacity improved.
Example 4
A method of increasing the activity of a noble metal catalyst comprising the steps of:
step 1, designing the molar ratio of copper ions in a metal salt solution to zinc atoms in a platinum alloy catalyst to be 9, selecting 1g of the platinum-zinc alloy catalyst, wherein the content of zinc is 20%, dispersing the platinum-zinc alloy catalyst in 270mL of 0.1mol/L copper nitrate solution, heating in a 70 ℃ water bath, and stirring for 3 hours to obtain a reaction product.
And 2, filtering and washing the reaction product, and drying in a forced air drying oven at 100 ℃ for 24 hours to obtain the platinum-zinc-copper alloy catalyst with copper added into the platinum-zinc alloy catalyst.
Example 5
A method of increasing the activity of a noble metal catalyst comprising the steps of:
step 1, designing the molar ratio of copper ions in a metal salt solution to cobalt atoms in a platinum alloy catalyst to be 0.1, selecting 1g of the platinum-cobalt alloy catalyst, wherein the cobalt content is 30%, dispersing the platinum-cobalt alloy catalyst in 50.9mL of 0.01mol/L copper nitrate solution, heating in a water bath at 70 ℃, and stirring for 3 hours to obtain a reaction product.
And 2, filtering and washing the reaction product, and drying in a forced air drying oven at 100 ℃ for 24 hours to obtain the platinum-zinc-copper alloy catalyst with copper added into the platinum-zinc alloy catalyst.
Example 6
A method of increasing the activity of a noble metal catalyst comprising the steps of:
step 1, designing the molar ratio of copper ions in a metal salt solution to cobalt atoms in a platinum alloy catalyst to be 13.7, selecting 1g of the platinum-cobalt alloy catalyst, wherein the cobalt content is 30%, dispersing the platinum-cobalt alloy catalyst in 23.2mL of copper nitrate solution with the concentration of 3mol/L, heating in a water bath at 50 ℃ and stirring for 6 hours to obtain a reaction product.
And 2, filtering and washing the reaction product, and drying in a forced air drying oven at 50 ℃ for 24 hours to obtain the platinum-zinc-copper alloy catalyst with copper added into the platinum-zinc alloy catalyst.
Example 7
A method of increasing the activity of a noble metal catalyst comprising the steps of:
step 1, designing the molar ratio of copper ions in a metal salt solution to cobalt atoms in a platinum alloy catalyst to be 5, selecting 1g of the platinum-cobalt alloy catalyst, wherein the cobalt content is 30%, dispersing the platinum-cobalt alloy catalyst in 17mL of 1.5mol/L copper nitrate solution, heating in a water bath at 90 ℃, and stirring for 0.5h to obtain a reaction product.
And 2, filtering and washing the reaction product, and drying in a blast drying oven at 120 ℃ for 24 hours to obtain the platinum-zinc-copper alloy catalyst with copper added into the platinum-zinc alloy catalyst.
XRD test and LSV electrochemical test were performed on the untreated platinum alloy catalyst and the platinum alloy catalyst obtained after the immersion heat treatment in the copper nitrate solution in example 2, and the data were collated to obtain fig. 1 and 2, respectively.
As can be seen from fig. 1, the diffraction peak of copper appears after the original platinum-nickel alloy catalyst in example 2 is subjected to the dipping heat treatment with the copper nitrate solution, which indicates that the copper element is successfully introduced into the original platinum-nickel alloy catalyst to obtain the platinum-nickel-copper alloy catalyst, and as can be seen from fig. 2, the platinum-nickel-copper alloy catalyst obtained through the treatment of example 2 has increased limiting current density and current density at a voltage of 0.9V compared with the platinum-nickel alloy catalyst, which indicates that the oxygen reduction activity of the catalyst is improved.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A method for improving the activity of a noble metal catalyst is characterized by comprising the following steps:
step S1, dipping a noble metal catalyst in a metal salt solution, and heating the solution; adding a metal contained in the metal salt solution to the noble metal catalyst by a reaction;
and step S2, carrying out solid-liquid separation, washing the filter residue with water, and drying to obtain a post-treatment product.
2. The method for increasing the activity of a noble metal catalyst according to claim 1,
the noble metal catalyst is a platinum alloy catalyst and comprises platinum metal and another more active metal which is more active than the platinum metal;
the metal salt solution can react with the more active metal to displace the more active metal, and the metal contained in the metal salt solution is added to the platinum alloy catalyst in the reaction process.
3. The method for increasing the activity of a noble metal catalyst according to claim 2,
the active metal in the platinum alloy catalyst is selected from one of cobalt, nickel, copper, manganese, zinc, magnesium and aluminum.
4. The method for increasing the activity of a noble metal catalyst according to claim 2,
the metal salt solution is selected from one or more of cobalt salt, nickel salt, copper salt, manganese salt, zinc salt, magnesium salt, aluminum salt and platinum salt.
5. The method for increasing the activity of a noble metal catalyst according to claim 2,
the molar ratio of the metal ions in the metal salt solution to the more active metal atoms in the platinum alloy catalyst is 0.1-13.7.
6. The method for increasing the activity of a noble metal catalyst according to claim 5,
the molar ratio of metal ions in the metal salt solution to more active metal atoms in the platinum alloy catalyst is 5-9.
7. The method for increasing the activity of a noble metal catalyst according to claim 2,
in step S1, the heating treatment mode is water bath, oil bath or metal bath; the heating temperature is 50-90 ℃; the heating time is 0.5-6 h.
8. The method for increasing the activity of a noble metal catalyst according to claim 7,
in step S1, the heating temperature is 70-90 ℃ and the heating time is 2-3 h.
9. The method for increasing the activity of a noble metal catalyst according to claim 2,
in step S2, the drying temperature is 50-120 ℃.
10. The method for increasing the activity of a noble metal catalyst according to claim 2,
the concentration of the metal salt solution is 0.01-3.00 mol/L.
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Citations (4)
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| CN101522345A (en) * | 2006-08-30 | 2009-09-02 | 尤米科尔股份公司及两合公司 | Core/shell-type catalyst particles comprising metal or ceramic core materials and methods for their preparation |
| CN101997123A (en) * | 2009-08-14 | 2011-03-30 | 济南美高纳米材料有限公司 | Nano porous alloy fuel battery catalyst and preparation method thereof |
| US20160359171A1 (en) * | 2015-06-02 | 2016-12-08 | Toyota Jidosha Kabushiki Kaisha | Method of producing core-shell catalyst |
| CN110858652A (en) * | 2018-08-23 | 2020-03-03 | 现代摩比斯株式会社 | Electrode catalyst for fuel cell and method for manufacturing the same |
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- 2021-07-12 CN CN202110782656.3A patent/CN113540475A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101522345A (en) * | 2006-08-30 | 2009-09-02 | 尤米科尔股份公司及两合公司 | Core/shell-type catalyst particles comprising metal or ceramic core materials and methods for their preparation |
| CN101997123A (en) * | 2009-08-14 | 2011-03-30 | 济南美高纳米材料有限公司 | Nano porous alloy fuel battery catalyst and preparation method thereof |
| US20160359171A1 (en) * | 2015-06-02 | 2016-12-08 | Toyota Jidosha Kabushiki Kaisha | Method of producing core-shell catalyst |
| CN110858652A (en) * | 2018-08-23 | 2020-03-03 | 现代摩比斯株式会社 | Electrode catalyst for fuel cell and method for manufacturing the same |
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Application publication date: 20211022 |