CN114300693A - Method for improving stability of fuel cell carbon-supported platinum-based catalyst through activation of carbon carrier - Google Patents
Method for improving stability of fuel cell carbon-supported platinum-based catalyst through activation of carbon carrier Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 87
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000004913 activation Effects 0.000 title claims description 14
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- 230000003213 activating effect Effects 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 6
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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Images
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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 discloses a method for improving the stability of a fuel cell carbon-supported platinum-based catalyst by activating a carbon carrier, which comprises the following steps: firstly, activating the surface of a carbon carrier by using strong base in an inert atmosphere at a high temperature to obtain an activated carbon carrier with a sunken pore structure on the surface; and (3) loading the platinum-based nanoparticles into the pores on the surface of the activated carbon carrier to obtain the high-stability fuel cell carbon-loaded platinum-based catalyst. The high-temperature treatment can improve the conductivity and corrosion resistance of the carbon carrier; the unique concave structure on the surface of the activated carbon carrier can generate a confinement effect on the nano particles, so that the stability of the catalyst is improved and the activity is not reduced. The method solves the problem that the activity of the existing fuel cell carbon-supported platinum-based catalyst is reduced due to the migration and agglomeration of platinum-based metal nanoparticles in a working environment, is simple to operate, and is suitable for large-scale preparation of the high-stability fuel cell carbon-supported platinum-based catalyst.
Description
Technical Field
The invention belongs to the technical field of new energy fuel cells, and particularly relates to a method for improving the stability of a fuel cell carbon-supported platinum-based catalyst through activation of a carbon carrier.
Background
Hydrogen energy is a clean, efficient, safe and sustainable secondary energy, and becomes the most promising substitute for fossil energy when the human society faces severe energy crisis and environmental pollution problems. The fuel cell uses hydrogen as fuel, can directly convert chemical energy into electric energy, has a series of advantages of environmental friendliness, high energy density, high energy conversion efficiency and the like, and is one of the most potential energy conversion devices at present. But the durability issues and slow cathode oxygen reduction reaction kinetics greatly limit the further development of fuel cells.
The insufficient durability of the fuel cell is mainly derived from the deterioration of the performance of the catalyst in the membrane electrode catalytic layer. The best performance is currently available and the most widely used fuel cell catalyst is the carbon-supported platinum catalyst. However, at the operating potential of the fuel cell, the carbon carrier of the carbon-supported platinum catalyst is easily corroded, and the platinum nanoparticles supported on the surface of the carbon carrier are easily dropped off and migrate and agglomerate, so that the platinum nanoparticles continuously grow up, and the performance of the catalyst is rapidly attenuated. Therefore, the method for enhancing the corrosion resistance of the carbon carrier and inhibiting the migration and aggregation of the nano-particles in the working environment has great significance for the further development of the fuel cell.
Chinese patent 202011605526.4 discloses a method for preparing a fuel cell catalyst with high durability, which is mainly to modify the surface of a carbon-supported platinum-based catalyst by forming an ultra-thin coating layer from a mixture of an oxide and a carbon-based compound. The method can effectively inhibit the migration and growth of the platinum-based nanoparticles on the surface of the carbon-based carrier, and remarkably improve the stability of the catalyst. But inevitably covers part of active sites, so that certain catalytic activity loss is caused, and the utilization rate of the noble metal platinum is reduced.
Chinese patent 201911405226.9 discloses a fuel cell catalyst, its preparation method and application in fuel cells. The method mainly comprises the steps of filling the high polymer into the inner pore channels of the carbon carrier, calcining and curing to modify the carbon carrier, thereby achieving the purpose of improving the durability of the catalyst. However, the high polymer and the surfactant used in the technical scheme are difficult to remove, and inevitably cause the reduction of the electrochemical performance of the catalyst.
Chinese patent 202110014101.4 discloses a fuel cell catalyst, a preparation method and an application thereof, the method mainly protects nanoparticles by precisely attaching and packaging a special structure of Pt-M alloy nanoparticles by nitrogen-doped carbon nanotubes, and migration and aggregation of the nanoparticles and erosion of the nanoparticles from the outside under the working condition of the fuel cell are prevented. However, the encapsulation and protection of the nanoparticles by the carbon-based carrier can cause partial coverage of the active centers by the carrier and gas diffusion blockage. In addition, the particle size of the nano particles prepared by the method is larger, and the utilization rate of the noble metal platinum is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for improving the stability of a fuel cell carbon-supported platinum-based catalyst by activating a carbon carrier.
In order to achieve the purpose, the invention adopts the following technical scheme:
firstly, activating the surface of a carbon carrier by using strong base in an inert atmosphere at a high temperature to obtain an activated carbon carrier with a sunken pore structure on the surface; and preparing platinum-based nano particles loaded on the surface of the activated carbon carrier to obtain the high-stability fuel cell carbon-loaded platinum-based electrocatalyst. The high-temperature treatment can improve the graphitization degree of the carbon carrier, thereby improving the conductivity and corrosion resistance of the carbon carrier; the sunken pore structure on the surface of the activated carbon carrier can generate a confinement effect on the nano particles, so that the platinum-based nano particles can be stably confined on the surface of the carbon carrier, and the purpose of improving the durability of the catalyst is achieved.
A method for improving the stability of a fuel cell carbon-supported platinum-based catalyst by activating a carbon support comprises the following steps:
1) preparing a strong base solution, adding a carbon carrier, fully stirring and dispersing to obtain a suspension, filtering, collecting the carbon carrier, and performing vacuum drying treatment;
2) carrying out high-temperature treatment on the carbon carrier obtained by the treatment in a nitrogen atmosphere, cooling to room temperature, washing with water, and drying to obtain an activated carbon carrier with a pore structure with the pore diameter of 1-3 nm on the surface;
3) and (3) loading the platinum-based nanoparticles on the surface of the activated carbon carrier to obtain the high-stability fuel cell carbon-loaded platinum-based catalyst.
Preferably, the platinum-based nanoparticles comprise platinum nanoparticles, an alloy formed by platinum and a transition metal or core-shell structure nanoparticles; preferably, the transition metal is at least one of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, molybdenum, ruthenium, rhodium, palladium, silver, gold, iridium.
Preferably, the carbon carrier comprises graphite, graphene, carbon black, porous carbon, nitrogen-doped porous carbon, carbon nanotubes and carbon nanofibers.
Preferably, the strong alkali solution in the step 1) comprises an aqueous solution, an alcohol solution and an alcohol-water mixed solution of potassium hydroxide and sodium hydroxide, and the concentration is 0.5-3 mol/L; the concentration of the carbon carrier in the suspension is 2-12 mg/mL, when the strong base is potassium hydroxide, the mass ratio of the potassium hydroxide to the carbon carrier is 5-15: 1. when the concentration of strong base in the suspension is too high, the carbon carrier surface is supersaturated in the adsorption mode, and a large amount of strong base remains in the filtrate, so that the cost is increased additionally; when the concentration of the carbon carrier is too high, the viscosity is too high, and the carbon carrier is not easy to disperse uniformly. Preferably, the concentration of the strong alkali solution is 0.5 mol/L, and the concentration of the carbon carrier is 2 mg/mL.
Preferably, the high-temperature treatment in the step 2) is 500-1500 ℃ high-temperature treatment for 5-15 h. When the heat treatment time is short, the activation effect is weak, the surface sunken hole structure is small, and an effective limited domain effect cannot be generated; when the heat treatment time is too long, the carbon support structure is easily damaged or the pore diameter of the surface pore structure is too large, so that the platinum-based nanoparticles are trapped inside the pores. The heat treatment temperature is preferably 750 ℃, the time is 5-15 h, and the pore size distribution of the surface pores is controlled to be 1-3 nm.
Preferably, the method for supporting platinum-based nanoparticles on the surface of the activated carbon support described in step 3) includes a liquid phase preparation method, a dipping reduction method, and a platinum loading amount of 5-80 wt%.
The method for improving the stability of the fuel cell carbon-supported platinum-based catalyst through carbon carrier activation has the following benefits:
1) according to the technical scheme, a pore structure with a proper pore diameter is constructed on the surface of the carbon carrier through activation treatment of the carbon carrier. The unique pore structure can generate a domain limiting effect, stabilize the nanoparticles on the surface of the carbon carrier, inhibit the falling and migration of the nanoparticles under the working condition of the fuel cell, and achieve the purpose of improving the stability of the catalyst.
2) According to the technical scheme, the activation of the carbon carrier is carried out by adopting a high-temperature heat treatment method, and the graphitization degree of the carbon carrier is improved while a concave hole structure is formed on the surface of the carbon carrier. The improvement of the graphitization degree can obviously improve the conductivity and the stability of the carbon carrier, and effectively relieve the corrosion of the harsh working environment of the fuel cell to the carbon carrier.
3) The technical scheme improves the durability of the catalyst and simultaneously avoids activity loss caused by covering the active center of the nano particles by the cladding layer in the prior art. The method is simple to operate, can be expanded to the preparation of other supported metal catalysts such as ruthenium, rhodium, palladium, silver, osmium, iridium and gold-based carbon materials, is easy for large-scale production, and has very important significance for solving the problem of insufficient durability of the fuel cell at present.
Drawings
FIG. 1 is a schematic diagram showing the pore size distribution of porous carbon carriers in example 1 and comparative examples 1, 2, 3 and 4 according to the present invention;
FIG. 2 is a comparison of cyclic voltammograms of example 2 of the present invention with comparative examples 5 and 6 before and after 30000 accelerated durability tests;
FIG. 3 is a graph showing the comparison between the polarization curve and the energy density curve before and after 10000 times and 30000 times of accelerated durability tests in example 2 of the present invention and comparative example 6.
Detailed Description
The present invention is further illustrated, but is not limited, by the following specific examples.
Example 1
Weighing 2 g of potassium hydroxide, dissolving the potassium hydroxide in 100 mL of water to prepare 0.5 mol/L potassium hydroxide solution, adding 0.2 g of nitrogen-doped porous carbon, fully stirring and dispersing for 20 hours to obtain suspension, standing until the suspension is fully precipitated, and then carrying out suction filtration. Vacuum drying the filter residue at 40 deg.C for 12 hr, and grinding the dried filter residue to obtain fine black powder. Adding black powder into a molybdenum crucible, and treating at 750 ℃ for 10 hours under a nitrogen atmosphere. And after cooling to room temperature, washing the carbon carrier powder for three times by water and drying to obtain the activated porous carbon carrier I.
Example 2
25 mg of platinum nanoparticles with the average size of 2 nm are prepared by adopting an ethylene glycol reduction method and are uniformly loaded on the surface of 100 mg of the porous carbon carrier I obtained in the example 1, so that the carbon-supported platinum catalyst I for the high-stability fuel cell is obtained.
Comparative example 1
Weighing 2 g of potassium hydroxide, dissolving the potassium hydroxide in 100 mL of water to prepare 0.5 mol/L potassium hydroxide solution, adding 0.2 g of nitrogen-doped porous carbon, fully stirring and dispersing for 20 hours to obtain suspension, standing until the suspension is fully precipitated, and then carrying out suction filtration. Vacuum drying the filter residue at 40 deg.C for 12 hr, and grinding the dried filter residue to obtain fine black powder. Adding black powder into a molybdenum crucible, and treating at 750 ℃ for 4 h under a nitrogen atmosphere. And after cooling to room temperature, washing the carbon carrier powder for three times by water and drying to obtain the activated porous carbon carrier II.
Comparative example 2
Weighing 2 g of potassium hydroxide, dissolving the potassium hydroxide in 100 mL of water to prepare 0.5 mol/L potassium hydroxide solution, adding 0.2 g of nitrogen-doped porous carbon, fully stirring and dispersing for 20 hours to obtain suspension, standing until the suspension is fully precipitated, and then carrying out suction filtration. Vacuum drying the filter residue at 40 deg.C for 12 hr, and grinding the dried filter residue to obtain fine black powder. Adding black powder into a molybdenum crucible, and carrying out high-temperature treatment at 750 ℃ for 16 h under a nitrogen atmosphere. And after cooling to room temperature, washing the carbon carrier powder for three times by water and drying to obtain the activated porous carbon carrier III.
Comparative example 3
Weighing 2 g of potassium hydroxide, dissolving the potassium hydroxide in 100 mL of water to prepare 0.5 mol/L potassium hydroxide solution, adding 0.2 g of nitrogen-doped porous carbon, fully stirring and dispersing for 20 hours to obtain suspension, standing until the suspension is fully precipitated, and then carrying out suction filtration. Vacuum drying the filter residue at 40 deg.C for 12 hr, and grinding the dried filter residue to obtain fine black powder. Adding black powder into a molybdenum crucible, and carrying out high-temperature treatment at 400 ℃ for 16 h under the nitrogen atmosphere. And after cooling to room temperature, washing the carbon carrier powder for three times by water and drying to obtain the activated porous carbon carrier IV.
Comparative example 4
Weighing 2 g of potassium hydroxide, dissolving the potassium hydroxide in 100 mL of water to prepare 0.5 mol/L potassium hydroxide solution, adding 0.2 g of nitrogen-doped porous carbon, fully stirring and dispersing for 20 hours to obtain suspension, standing until the suspension is fully precipitated, and then carrying out suction filtration. Vacuum drying the filter residue at 40 deg.C for 12 hr, and grinding the dried filter residue to obtain fine black powder. Adding black powder into a molybdenum crucible, and carrying out high-temperature treatment at 1600 ℃ for 5 h under the nitrogen atmosphere. And after cooling to room temperature, washing the carbon carrier powder for three times by water and drying to obtain the activated porous carbon carrier V.
It can be seen from the comparison of pore size distribution in fig. 1 that the proportion of pores with a pore size of 1-3 nm of the porous carbon carrier i is significantly increased when the porous carbon carrier i is activated for 10 hours in example 1, and the larger pore size can provide an effective domain limiting effect and inhibit the falling and migration of particles; in comparative example 1, the activation treatment time is too short, the pore size distribution of the obtained carbon carrier is mainly concentrated at 0.5-1 nm, and the too small pore size cannot provide effective confinement effect; in comparative example 2, the pore size distribution of the carbon support was instead concentrated below 1 nm due to collapse of the carbon support structure caused by excessively long activation time. In comparative examples 3 and 4, the activation temperature is respectively reduced and increased, when the temperature is too low, the reaction is too slow, the pore diameter is still not mainly concentrated in the range of 1-3 nm after the treatment for 16 hours, and when the temperature is too high, the reaction is too violent, so that the porous carbon carrier structure is easy to collapse.
Comparative example 5
25 mg of platinum nanoparticles with the average size of 2 nm are prepared by adopting an ethylene glycol reduction method, and are uniformly loaded on the surface of a porous carbon carrier II obtained in 100 mg of comparative example 1, so that the carbon-supported platinum catalyst II for the fuel cell is obtained.
Comparative example 6
Commercial platinum carbon catalyst.
Electrochemical performance test
In each of the examples and comparative examples, 4 mg of each of the fuel cell catalysts was taken, 590. mu.L of water, 1.39 mL of isopropyl alcohol, and 20. mu.L of nafion solution (Dupont, USA) were added, and ultrasonic dispersion was performed for 5 min to prepare a catalyst slurry, and 10. mu.L of the catalyst slurry was coated on the surface of a rotating disk electrode having a diameter of 5 mm to form a working electrode.
Taking a platinum sheet electrode as a counter electrode and a saturated silver chloride electrode as a reference electrode, and carrying out accelerated durability test in 0.1 mol/L perchloric acid electrolyte, wherein the test potential interval is 0.6-0.95V (vs. RHE), and the sweep rate is 50 mV/s.
FIG. 2 is a graph showing the comparison of cyclic voltammograms and mass activities before and after accelerated durability tests in example 2, comparative example 5 and comparative example 6 of the present invention. Example 2 the electrochemical active area decay phenomenon before and after 30000 cycles was significantly improved over the comparative example and a higher proportion of mass activity was maintained. The activated carbon carrier has obvious effects on inhibiting the migration of metal nano particles and improving the stability of the catalyst.
The cell assembly of example 2 and comparative example 6 was tested. The catalyst obtained in example 2 of the present invention and the comparative example were used to prepare a catalyst membrane having an area of 5 × 5 cm, and a single cell was assembled. Accelerated durability tests were conducted according to the test methods established by the U.S. department of energy, accelerated aging of the catalyst at 0.6-0.95V, and polarization curve and energy density curve tests were conducted at 10000 and 30000 cycles of accelerated aging. Fig. 3 shows the polarization curve and energy density curve of example 2 and comparative example 6 before and after 10000 and 30000 cycles. 30000 cycles cause significant loss of fuel cell activity, but the current density and maximum energy density decay phenomenon of the fuel cell assembled in example 2 after cycles are significantly improved compared with those of comparative example 6, which shows that the invention has great significance for solving the durability problem of the fuel cell.
The above examples are merely for clearly illustrating the present invention, and the embodiments of the present invention are not limited thereto. Any modification, replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (8)
1. A method for improving the stability of a fuel cell carbon-supported platinum-based catalyst through carbon carrier activation is characterized by comprising the following steps: firstly, activating a carbon carrier to obtain an activated carbon carrier with a sunken pore structure on the surface; and loading platinum-based nano particles into pores on the surface of the activated carbon carrier to obtain the high-stability fuel cell carbon-loaded platinum-based electrocatalyst.
2. The method of activating a carbon support to improve the stability of a platinum on carbon based catalyst for a fuel cell according to claim 1, comprising the steps of:
1) preparing a strong base solution, adding a carbon carrier, fully stirring and dispersing to obtain a suspension, filtering, collecting the carbon carrier, and performing vacuum drying treatment;
2) carrying out high-temperature treatment on the carbon carrier obtained by the treatment in the step 1) in a nitrogen atmosphere, cooling to room temperature, washing with water, and drying to obtain an activated carbon carrier with a pore structure with the pore diameter of 1-3 nm on the surface;
3) and (3) loading the platinum-based nanoparticles on the surface of the activated carbon carrier to obtain the high-stability fuel cell carbon-loaded platinum-based catalyst.
3. The method for improving the stability of the fuel cell platinum-on-carbon catalyst through the activation of the carbon support according to claim 1, wherein the platinum-based nanoparticles comprise platinum nanoparticles, an alloy formed by platinum and a transition metal, or core-shell structured nanoparticles.
4. The method of activating a carbon support to improve the stability of a platinum-on-carbon catalyst for a fuel cell according to claim 3, wherein the transition metal is at least one of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, molybdenum, ruthenium, rhodium, palladium, silver, gold, iridium.
5. The method for improving the stability of the fuel cell carbon-supported platinum-based catalyst through the activation of the carbon support according to claim 1 or 2, wherein the carbon support comprises graphite, graphene, carbon black, porous carbon, nitrogen-doped porous carbon, carbon nanotubes and carbon nanofibers.
6. The method for improving the stability of the platinum-on-carbon catalyst of the fuel cell by activating the carbon support according to claim 2, wherein the strong alkaline solution in the step 1) comprises an aqueous solution, an alcohol solution and an alcohol-water mixed solution of potassium hydroxide and sodium hydroxide, and the concentration of the solution is 0.5-3 mol/L; the concentration of the carbon carrier in the suspension is 2-12 mg/mL.
7. The method for improving the stability of the fuel cell carbon-supported platinum-based catalyst through the activation of the carbon support as claimed in claim 2, wherein the high temperature treatment in the step 2) is high temperature treatment at 500-1500 ℃ for 5-15 h.
8. The method for improving the stability of the fuel cell carbon-supported platinum-based catalyst by activating the carbon support according to claim 2, wherein the method for supporting the platinum-based nanoparticles on the surface of the activated carbon support in the step 3) comprises a liquid phase preparation method and an impregnation reduction method, and the platinum loading is 5-80 wt%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114937784A (en) * | 2022-06-28 | 2022-08-23 | 湖南清牛新材料科技有限公司 | Carbon-carried platinum-cobalt alloy catalyst for proton exchange membrane fuel cell and preparation method thereof |
| CN115212905A (en) * | 2022-06-29 | 2022-10-21 | 浙江新和成股份有限公司 | Selective hydrogenation catalyst for alkynol and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583550A (en) * | 2004-06-11 | 2005-02-23 | 中国科学院山西煤炭化学研究所 | Preparing method for porous carbon with high specific surface area |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
| CN111106357A (en) * | 2019-12-16 | 2020-05-05 | 江苏大学 | Preparation method and application of platinum-based catalyst based on etching treatment of carbon carrier |
| CN111224112A (en) * | 2020-01-10 | 2020-06-02 | 中自环保科技股份有限公司 | Preparation method of electrocatalyst for hydrogen fuel cell |
| CN111250158A (en) * | 2019-11-29 | 2020-06-09 | 浙江工业大学 | Carbon-supported alkaline ionic liquid-metal catalyst and preparation and application thereof |
| CN113707889A (en) * | 2021-08-09 | 2021-11-26 | 清华大学深圳国际研究生院 | Carbon-supported platinum nano catalyst, preparation method thereof, catalyst layer and proton exchange membrane fuel cell |
-
2021
- 2021-12-30 CN CN202111638263.1A patent/CN114300693B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583550A (en) * | 2004-06-11 | 2005-02-23 | 中国科学院山西煤炭化学研究所 | Preparing method for porous carbon with high specific surface area |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
| CN111250158A (en) * | 2019-11-29 | 2020-06-09 | 浙江工业大学 | Carbon-supported alkaline ionic liquid-metal catalyst and preparation and application thereof |
| CN111106357A (en) * | 2019-12-16 | 2020-05-05 | 江苏大学 | Preparation method and application of platinum-based catalyst based on etching treatment of carbon carrier |
| CN111224112A (en) * | 2020-01-10 | 2020-06-02 | 中自环保科技股份有限公司 | Preparation method of electrocatalyst for hydrogen fuel cell |
| CN113707889A (en) * | 2021-08-09 | 2021-11-26 | 清华大学深圳国际研究生院 | Carbon-supported platinum nano catalyst, preparation method thereof, catalyst layer and proton exchange membrane fuel cell |
Non-Patent Citations (3)
| Title |
|---|
| YU ZHU: ""Highly Exposed Active Sites of Defect-Enriched Derived MOFs for Enhanced Oxygen Reduction Reaction"", 《ACS SUSTAINABLE CHEM. ENG.》, vol. 7, pages 17855 * |
| 栗云彦: ""活性炭载体的改性对钯炭催化剂性能的影响研究进展"", 《贵金属》, vol. 34, no. 3, pages 82 - 86 * |
| 梁秋霞: ""Pd/C催化剂载体表面微环境与前驱体吸附行为研究"", 《中国博士学位论文全文数据库 工程科技I辑》, vol. 11, pages 014 - 166 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114937784A (en) * | 2022-06-28 | 2022-08-23 | 湖南清牛新材料科技有限公司 | Carbon-carried platinum-cobalt alloy catalyst for proton exchange membrane fuel cell and preparation method thereof |
| CN115212905A (en) * | 2022-06-29 | 2022-10-21 | 浙江新和成股份有限公司 | Selective hydrogenation catalyst for alkynol and preparation method and application thereof |
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