CN112838223A - Preparation method and application of fuel cell catalyst with rod-shaped manganese dioxide as promoter - Google Patents
Preparation method and application of fuel cell catalyst with rod-shaped manganese dioxide as promoter Download PDFInfo
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- CN112838223A CN112838223A CN202110013594.XA CN202110013594A CN112838223A CN 112838223 A CN112838223 A CN 112838223A CN 202110013594 A CN202110013594 A CN 202110013594A CN 112838223 A CN112838223 A CN 112838223A
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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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- 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
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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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 relates to a preparation method of a fuel cell catalyst with rod-shaped manganese dioxide as an accelerant, which comprises the following steps: (1) preparing manganese dioxide with a rod-like shape by a hydrothermal method; (2) under an alkaline condition, simultaneously reducing graphene oxide and a metal precursor by a heating reflux method to prepare a metal/graphene catalyst; (3) adding the manganese dioxide prepared in the step (1) into the catalyst prepared in the step (2), and ultrasonically and uniformly mixing to obtain a finished product catalyst. According to the invention, the rodlike manganese dioxide modified Pd (Pt) graphene composite catalyst is synthesized for the first time, the introduction of the manganese dioxide can generate interaction with noble metal Pd (Pt), and the catalytic activity of the catalyst is improved by changing the electronic structure of Pd (Pt).
Description
Technical Field
The invention belongs to the technical field of fuel cell catalysts, and particularly relates to a preparation method and application of a fuel cell catalyst taking rod-shaped manganese dioxide as an accelerator.
Background
In recent years, the energy crisis and environmental pollution have seriously hindered the sustainable development of human beings. Therefore, the development of new and environmentally friendly energy sources is urgently needed. The fuel cell as a novel energy conversion device has the advantages of high energy conversion efficiency, convenience in carrying and the like, so that the fuel cell has wide application prospects in the fields of electric automobiles, mobile power sources, clean power stations and the like, and the great development of the fuel cell technology is very important. The noble metals Pt and Pd are the anode catalyst materials of the direct alcohol fuel cell with the best performance and the most extensive application at present. However, since the electrochemical oxidation process of small alcohol molecules is complicated, many reaction intermediate products can be adsorbed on the surfaces of Pt and Pd, so that the Pt and Pd are poisoned and deactivated, and the Pt and Pd are scarce in resources and expensive, thereby greatly restricting the development and application of fuel cell technology. Therefore, reducing the amount of pt (pd) and developing other low-cost, high-performance catalysts are key technologies to advance the development of fuel cell industrialization.
The invention patent with the publication number of CN 104998642B specifically discloses a preparation method of an alcohol fuel cell anode catalyst, which comprises three steps of preparing graphene nanoribbons, modifying the graphene nanoribbons with manganese dioxide and loading palladium nanoparticles on the graphene nanoribbons with manganese dioxide to prepare the alcohol fuel cell anode catalyst. The preparation method of the patent requires high temperature and freeze drying, conditions are harsh, meanwhile, a stabilizer is added in the preparation process, so that metal nanoparticles such as palladium and the like are uniformly dispersed, the stabilizer is easily adsorbed on the surface of the catalyst, and the catalytic performance of the catalyst is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method and application of a fuel cell catalyst taking rod-shaped manganese dioxide as an accelerant.
In order to solve the technical problems, the invention adopts a technical scheme that:
a preparation method of a fuel cell catalyst taking rod-shaped manganese dioxide as an accelerant comprises the following steps:
(1) preparing manganese dioxide with a rod-like shape by a hydrothermal method;
(2) under an alkaline condition, simultaneously reducing graphene oxide and a metal precursor by a heating reflux method to prepare a metal/graphene catalyst;
(3) and (3) adding the manganese dioxide prepared in the step (1) into the catalyst prepared in the step (2), and ultrasonically mixing uniformly to obtain a target catalyst, namely the fuel cell catalyst taking rod-shaped manganese dioxide as an accelerator.
Preferably, the metal precursor in step (2) is a palladium precursor or a platinum precursor.
Preferably, the specific operation of step (1) is: uniformly stirring potassium permanganate, manganese sulfate and deionized water, transferring the mixture into a reaction kettle, reacting for 24-48 h at the hydrothermal temperature of 120-180 ℃, naturally cooling, centrifuging, washing and drying in vacuum to obtain the manganese dioxide solid with the rod-shaped appearance.
Further preferably, the molar ratio of potassium permanganate to manganese sulfate is 0.67: 1-5: 1.
Preferably, the platinum precursor is one of chloroplatinic acid hexahydrate, potassium hexachloroplatinate and potassium tetrachloroplatinate; the palladium precursor is one of palladium chloride, palladium nitrate, palladium acetate, potassium hexachloropalladate and potassium tetrachloropalladate.
Preferably, the alkaline condition in step (2) is to adjust the pH to 9-13 with sodium hydroxide or potassium hydroxide.
Preferably, in the step (2), the loading of palladium or platinum is 10-40 wt%.
Preferably, in the step (2), the reflux reaction is carried out at the temperature of 120-160 ℃ for 4-8 h.
Preferably, in the step (3), the mass ratio of the manganese dioxide to the graphene is 1: 5-5: 1.
Preferably, after the reaction in the step (2) is finished, ethanol and deionized water are sequentially used for centrifugal cleaning for 3-5 times, then deionized water is added, and volume is determined after ultrasonic uniform, so that palladium (platinum)/graphene catalyst stock solution is obtained for standby.
Preferably, in the step (3), the manganese dioxide and Nafion solution (0.5 wt%) prepared in the step (1) are added to the palladium (platinum)/graphene catalyst stock solution prepared in the step (2), and the mixture is ultrasonically mixed to obtain the target catalyst.
In order to solve the above technical problems, the present invention adopts another technical solution:
a fuel cell catalyst using rod-shaped manganese dioxide as a promoter was prepared according to the above preparation method.
The fuel cell catalyst which is prepared by the preparation method and takes the rod-shaped manganese dioxide as the promoter is applied to the fuel cell anode catalyst.
Preferably, the fuel cell catalyst prepared by the preparation method takes the rod-shaped manganese dioxide as a promoter and is applied to the catalytic oxidation of ethylene glycol.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention has novel design scheme, and synthesizes the rodlike manganese dioxide modified Pd (Pt) graphene composite catalyst for the first time, the introduction of the manganese dioxide can generate interaction with noble metal Pd (Pt), and the catalytic activity of the catalyst is improved by changing the electronic structure of Pd (Pt);
2. the reagent used in the invention is environment-friendly, safe and environment-friendly;
3. the operation method is simple and easy to implement, mild in reaction condition, low in equipment requirement and suitable for large-scale production;
4. the noble metal nano particles prepared by the method are uniformly dispersed, and no surfactant is added in the preparation process, so that the influence of the surfactant on the catalytic activity of the noble metal catalyst is effectively avoided;
5. the catalyst prepared by the invention can improve the utilization rate of noble metal Pd (Pt), has high electrocatalytic performance and stability, and can be widely applied to electrocatalytic oxidation of organic micromolecules such as methanol, ethanol, glycol, glycerol, formic acid and the like.
Drawings
FIG. 1 shows Pd/MnO prepared in example 1 of the present invention2-transmission electron micrograph of the GE-1 catalyst;
FIG. 2 shows Pd/MnO prepared in example 1 of the present invention2-cyclic voltammogram of electrocatalytic oxidation of ethylene glycol by GE-1 catalyst and Pd/GE catalyst prepared in comparative example 1;
FIG. 3 is Pd/MnO prepared in example 1 of the present invention2-GE-1 catalyst, Pd/MnO prepared in example 22-GE-2 catalyst and Pd prepared in example 3MnO2-cyclic voltammogram of electrocatalytic oxidation of ethylene glycol by the GE-3 catalyst;
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments. The following examples were conducted in accordance with conventional methods and conditions, and experimental methods without specifying specific conditions were used.
Example 1
The preparation method of the fuel cell catalyst using the rod-shaped manganese dioxide as the promoter in this embodiment includes the following steps:
(1) manganese dioxide (MnO)2) The preparation of (1): weighing 3g of manganese sulfate and 7.9g of potassium permanganate, dissolving in 100mL of deionized water, ultrasonically dispersing, transferring to a reaction kettle, reacting for 24 hours at 160 ℃, naturally cooling to room temperature, centrifugally cleaning with deionized water, finally transferring the centrifugal precipitate to a vacuum drying oven, and carrying out vacuum drying overnight at 60 ℃ to obtain the rod-shaped manganese dioxide solid.
(2) Preparing Graphene (GE) supported palladium nanoparticles: weighing 0.04g of graphene oxide, adding the graphene oxide into 40mL of deionized water, and performing ultrasonic dispersion for 1-2 hours to obtain a brown-yellow graphene oxide suspension; then adding 4mL (4mg/mL) of chloropalladite solution and 40mL of glycol, and adjusting the pH of the mixed system to 10 by using sodium hydroxide solution; then transferring the mixture into an oil bath, heating the mixture to 130 ℃, and carrying out reflux reaction for 6 h; after the reaction is finished, naturally cooling to room temperature, centrifugally cleaning for 3-5 times by using ethanol and deionized water in sequence, and ultrasonically dispersing the centrifugal product into 80mL of deionized water to prepare the graphene-supported palladium nanoparticle catalyst stock solution.
(3) Graphene-supported palladium nanoparticles (Pd/MnO) with rodlike manganese dioxide as promoter2-GE) preparation of the catalyst: weighing 2.5mg of MnO prepared in step (1)2Adding the solution into 5mL of the Pd/GE solution prepared in the step (2), adding 2mL of Nafion solution (0.5 wt%), and performing ultrasonic treatment for 1h to obtain a target catalyst named as Pd/MnO2-GE-1 catalyst.
(4) Preparation of a working electrode: 10 mu L of Pd/MnO was pipetted with a pipette2Dripping the-GE-1 catalyst dispersion liquid on the surface of a clean and dry glassy carbon electrode, and naturally airingAnd then, the user is ready for use.
(5) And (3) electrochemical performance testing: performing an experiment by using a three-electrode system, wherein a glassy carbon electrode (the diameter is 3mm) is used as a working electrode, and the preparation method of the working electrode refers to the step (4); a platinum wire electrode (diameter 0.5mm) and a saturated calomel electrode were used as a counter electrode and a reference electrode, respectively. And (3) testing conditions are as follows: the scanning range is-0.8-0.1V, the scanning speed is 50mV/s, and the solution is 1.0M potassium hydroxide +1.0M ethylene glycol.
FIG. 1 shows Pd/MnO prepared in this example2Transmission electron micrograph of the GE-1 catalyst. From FIG. 1, it can be seen that Pd nanoparticles are uniformly dispersed on the surface of GE and physically adsorbed with MnO2And (4) successfully compounding. FIG. 2 shows Pd/MnO prepared in this example2Cyclic voltammograms of the electrocatalytic oxidation of ethylene glycol by the GE-1 catalyst. As can be seen from FIG. 2, the Pd/MnO prepared is comparable to the Pd/GE catalyst2the-GE-1 catalyst exhibited high electrocatalytic properties for ethylene glycol, confirming that MnO2The cocatalyst function of (1).
Example 2
The preparation method and the specific operation procedure of the catalyst of this example were the same as those of example 1 except that MnO in step (3) was added2The addition amount of (A) was changed to 0.8mg, and the obtained catalyst was named Pd/MnO2-GE-2。
Example 3
The preparation method and the specific operation procedure of the catalyst of this example were the same as those of example 1 except that MnO in step (3) was added2The addition amount of (A) was changed to 7.5mg, and the obtained catalyst was named Pd/MnO2-GE-3。
FIG. 3 is Pd/MnO as catalyst prepared in example 12Catalyst Pd/MnO prepared in example 2 of GE-12-GE-2 and Pd/MnO as catalyst prepared in example 32Cyclic voltammograms of the electrocatalytic oxidation of ethylene glycol by GE-3. As can be seen from FIG. 3, MnO2The amount of (A) has a great influence on the catalytic performance of the catalyst, MnO2When the addition amount of (2.5 mg), the catalyst is Pd/MnO2The catalytic performance of the-GE-1 is optimal.
Comparative example
Preparation of the catalyst of this comparative example and the specific procedure the catalyst obtained was named Pd/GE according to example 1, except that MnO2 was not added.
It can be seen from the above examples and comparative examples that the invention can effectively improve the catalytic performance of the active ingredient Pd of the catalyst on ethylene glycol.
The present invention has been described in detail, and the embodiments are only used for understanding the method and the core idea of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and to implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a fuel cell catalyst taking rod-shaped manganese dioxide as an accelerant is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing manganese dioxide with a rod-like shape by a hydrothermal method;
(2) under an alkaline condition, simultaneously reducing graphene oxide and a metal precursor by a heating reflux method to prepare a metal/graphene catalyst;
(3) and (3) adding the manganese dioxide prepared in the step (1) into the catalyst prepared in the step (2), and ultrasonically mixing uniformly to obtain a target catalyst, namely the fuel cell catalyst taking rod-shaped manganese dioxide as an accelerator.
2. The method of claim 1, wherein the rod-shaped manganese dioxide is used as a promoter for a fuel cell catalyst, the method comprising: the metal precursor in the step (2) is a palladium precursor or a platinum precursor.
3. The method of claim 2, wherein the rod-shaped manganese dioxide is used as a promoter for a fuel cell catalyst, the method comprising: the specific operation of the step (1) is as follows: uniformly stirring potassium permanganate, manganese sulfate and deionized water, transferring the mixture into a reaction kettle, reacting at the hydrothermal temperature of 120-180 ℃ for 24-48 h, naturally cooling, centrifuging, washing and vacuum drying to obtain a rod-shaped manganese dioxide solid.
4. A method for preparing a fuel cell catalyst using rod-shaped manganese dioxide as a promoter according to claim 3, wherein: the molar ratio of the potassium permanganate to the manganese sulfate is 0.67: 1-5: 1.
5. The method of claim 2, wherein the rod-shaped manganese dioxide is used as a promoter for a fuel cell catalyst, the method comprising: the platinum precursor is one of chloroplatinic acid hexahydrate, potassium hexachloroplatinate and potassium tetrachloroplatinate; the palladium precursor is one of palladium chloride, palladium nitrate, palladium acetate, potassium hexachloropalladate and potassium tetrachloropalladate.
6. The method of claim 2, wherein the rod-shaped manganese dioxide is used as a promoter for a fuel cell catalyst, the method comprising: and (3) adjusting the pH to 9-13 by using sodium hydroxide or potassium hydroxide under the alkaline condition in the step (2).
7. The method of claim 2, wherein the rod-shaped manganese dioxide is used as a promoter for a fuel cell catalyst, the method comprising: in the step (2), the loading capacity of palladium or platinum is 10-40 wt%.
8. The method of claim 2, wherein the rod-shaped manganese dioxide is used as a promoter for a fuel cell catalyst, the method comprising: in the step (2), the temperature of the reflux reaction is 120-160 ℃, and the time is 4-8 h.
9. The method of claim 2, wherein the rod-shaped manganese dioxide is used as a promoter for a fuel cell catalyst, the method comprising: in the step (3), the mass ratio of the added manganese dioxide to the graphene is 1: 5-5: 1.
10. The use of a fuel cell catalyst comprising rod-shaped manganese dioxide as a promoter, prepared by the method according to any one of claims 1 to 9, as a fuel cell anode catalyst.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114400338A (en) * | 2022-03-25 | 2022-04-26 | 中国科学院过程工程研究所 | Mn-PtM/C type platinum-based oxygen reduction catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54139896A (en) * | 1978-04-24 | 1979-10-30 | Nippon Steel Corp | Production of manganese dioxide catalyst |
| CN104998642A (en) * | 2015-07-23 | 2015-10-28 | 上海电力学院 | Preparation method for alcohol fuel zincode catalyst Pd-MnO2/GNRs |
| CN105977501A (en) * | 2016-05-19 | 2016-09-28 | 中南大学 | High-performance oxygen reduction MnO2-Mn3O4/carbon nanotube composite catalyst and preparation method and application thereof |
-
2021
- 2021-01-06 CN CN202110013594.XA patent/CN112838223A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54139896A (en) * | 1978-04-24 | 1979-10-30 | Nippon Steel Corp | Production of manganese dioxide catalyst |
| CN104998642A (en) * | 2015-07-23 | 2015-10-28 | 上海电力学院 | Preparation method for alcohol fuel zincode catalyst Pd-MnO2/GNRs |
| CN105977501A (en) * | 2016-05-19 | 2016-09-28 | 中南大学 | High-performance oxygen reduction MnO2-Mn3O4/carbon nanotube composite catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| FANGFANG REN等: "Rod-like MnO2 boost Pd/reduced graphene oxide nanocatalyst for ethylene glycol electrooxidation", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 向斌 等: "《二维过渡金属化合物》", 28 February 2017 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114400338A (en) * | 2022-03-25 | 2022-04-26 | 中国科学院过程工程研究所 | Mn-PtM/C type platinum-based oxygen reduction catalyst and preparation method and application thereof |
| CN114400338B (en) * | 2022-03-25 | 2022-06-28 | 中国科学院过程工程研究所 | Mn-PtM/C type platinum-based oxygen reduction catalyst and preparation method and application thereof |
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Application publication date: 20210525 |