CN112713280A - Preparation method of noble metal platinum-based redox catalyst carrier - Google Patents

Preparation method of noble metal platinum-based redox catalyst carrier Download PDF

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CN112713280A
CN112713280A CN202011564423.8A CN202011564423A CN112713280A CN 112713280 A CN112713280 A CN 112713280A CN 202011564423 A CN202011564423 A CN 202011564423A CN 112713280 A CN112713280 A CN 112713280A
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noble metal
redox catalyst
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metal platinum
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杨书廷
尹艳红
牛富全
李向南
董红玉
岳红云
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Henan Normal University
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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
    • 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
    • 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
    • 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 noble metal platinum-based redox catalyst carrier, belonging to the technical field of electrocatalysis. The preparation method of the noble metal platinum-based redox catalyst carrier comprises the following steps: carrying out solvothermal reaction on nitrogen-doped porous carbon and a metal oxide source under an acidic condition; the metal oxide source is one or any combination of a titanium oxide source, a molybdenum oxide source and a tungsten oxide source. According to the preparation method of the noble metal platinum-based redox catalyst carrier, metal oxides are uniformly dispersed on carbon-doped porous carbon in situ by adopting a solvothermal method, so that the stability of the catalyst can be obviously improved, and 20000s durability tests show that the stability of the noble metal platinum-based redox catalyst adopting the carrier is obviously superior to that of a commercial platinum-carbon catalyst, and the noble metal platinum-based redox catalyst carrier has a good application prospect in the practical process of proton exchange membrane fuel cells and zinc air cells.

Description

Preparation method of noble metal platinum-based redox catalyst carrier
Technical Field
The invention relates to a preparation method of a noble metal platinum-based redox catalyst carrier, belonging to the technical field of electrocatalysis.
Background
The oxygen reduction reaction is the core reaction in proton exchange membrane fuel cells and metal-oxygen/air cells, and largely determines the efficiency of these cells. However, since the kinetics of the oxygen reduction reaction are slow, there is a serious problem of polarization, which seriously hinders their wide application. To date, carbon supported platinum (typical commercial catalysts platinum particle sizes of 3-5nm) catalyst materials are the most effective catalysts in both basic and acidic solutions. However, the weak interaction between the carbon support and the Pt nanoparticles results in dissolution, re-deposition and aggregation of these platinum nanoparticles, thereby reducing the electrochemically active surface area of the catalyst, ultimately leading to failure of the battery. The problem of corrosion of carbon supports has been a challenging research topic in the commercialization of oxygen reduction catalysts.
Currently, much research has focused on enhancing the interaction between platinum nanoparticles and support materials to improve the stability of oxygen reduction catalysts. The main methods are heteroatom doped carbon carriers, such as nitrogen, boron, phosphorus, sulfur, and the like, especially nitrogen doping, which can increase the polarity of the carbon material and thus enhance its interaction with platinum. In the prior art, the chinese patent application with application publication No. CN103346331A discloses a palladium/titanium dioxide/graphene catalyst, the catalyst is prepared by adding titanide into graphene oxide suspension to undergo hydrolysis reaction, and TiO in the carrier2The catalyst is covered on the surface of graphene to solve the problem of corrosion of graphene, but the stability of the catalyst still has a larger promotion space.
Disclosure of Invention
The invention aims to provide a preparation method of a noble metal platinum-based redox catalyst carrier, and the carrier prepared by the method can obviously improve the stability of the noble metal platinum-based redox catalyst.
In order to achieve the above object, the preparation method of the noble metal platinum-based redox catalyst carrier of the present invention adopts the following technical scheme:
a preparation method of a noble metal platinum-based redox catalyst carrier comprises the following steps: carrying out solvothermal reaction on nitrogen-doped porous carbon and a metal oxide source under an acidic condition; the metal oxide source is one or any combination of a titanium oxide source, a molybdenum oxide source and a tungsten oxide source.
According to the preparation method of the noble metal platinum-based redox catalyst carrier, the metal oxide is uniformly dispersed on the carbon-doped porous carbon in situ by adopting a solvothermal method, so that the adhesive force of the metal oxide on the nitrogen-doped porous carbon can be improved, the surface area of the metal oxide can be increased, and the uniform dispersion degree and the adhesive force of the noble metal on the carrier are remarkably improved by utilizing the strong interaction between the noble metal and the oxide, so that the stability of the catalyst is improved. 20000s durability test shows that the noble metal platinum-based redox catalyst adopting the carrier of the invention has stability obviously superior to commercial platinum-carbon catalyst, and has good application prospect in the practical process of proton exchange membrane fuel cells and zinc air cells.
Preferably, the mass ratio of the metal oxide to the nitrogen-doped porous carbon is 5-30: 70-95, based on the mass of the metal oxide formed by the solvothermal reaction of the metal oxide source. That is to say, the mass ratio of the metal oxide to the nitrogen-doped porous carbon in the prepared noble metal platinum-based redox catalyst carrier is 5-30: 70-95.
In order to suppress hydrolysis of the metal oxide source more preferably, the pH of the acidic condition is 3 to 6.
Preferably, the solvothermal reaction of nitrogen-doped porous carbon and a metal oxide source under acidic conditions comprises the steps of: dispersing nitrogen-doped porous carbon in a solvent, adding a pH regulator to adjust the system to be acidic, adding a metal oxide source, and then carrying out solvothermal reaction. The pH regulator is one of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the solvent used in the solvothermal reaction is an alcohol solvent. The alcohol solvent is preferably one or any combination of ethanol, isopropanol and n-propanol. The mass ratio of the nitrogen-doped porous carbon to the solvent is 1: 50.
The metal oxide source employed in the present invention can decompose at the temperature of the solvothermal reaction to produce the corresponding metal oxide. Preferably, the titanium oxide source is selected from one or any combination of titanate and titanium tetrachloride. The molybdenum oxide source is selected from one or any combination of ammonium molybdate and sodium molybdate. The tungsten oxide source is selected from one or any combination of ammonium tungstate and sodium tungstate. Preferably, the phthalate ester is selected from one or any combination of tetrabutyl titanate, tetraethyl titanate and isopropyl titanate.
Preferably, the nitrogen-doped porous carbon is prepared by the following steps: and (2) uniformly dispersing the carbon source, the nitrogen source and the template agent in water, removing water, performing pyrolysis reaction in an inert atmosphere, washing away the template agent, and drying to obtain the carbon-based composite material. The method has the advantages that in the process of preparing the nitrogen-doped porous carbon, the nitrogen-doped carbon nanosheets are mutually staggered and entangled to form a three-dimensional network structure as a framework, and finally the three-dimensional cross-linked nitrogen-doped carbon nanosheets are obtained. In addition, the template agent adopted by the method for preparing the nitrogen-doped porous carbon can be recycled, and the method is environment-friendly and is beneficial to preparing a large amount of oxygen reduction catalyst materials.
Conventional effluent treatment modes can be adopted, but in order to obtain the three-dimensional cross-linked nitrogen-doped carbon nanosheets with better appearance, the water removal treatment is preferably freeze drying.
Preferably, in the method for producing nitrogen-doped porous carbon, the temperature of the drying treatment performed after the template is washed off is 80 ℃.
The carbon source and the nitrogen source are both organic compounds. Preferably, the carbon source is preferably a carbohydrate. The carbon source is selected from one or any combination of glucose and sucrose. The nitrogen source is selected from one or any combination of urea and melamine.
Typically, the templating agent is a soluble salt and does not decompose at the pyrolysis temperature. Preferably, the template agent is selected from one or any combination of sodium chloride, sodium silicate with or without crystal water. The sodium chloride and the sodium silicate can be recycled, and are cheap, so that the preparation cost of the carrier is greatly reduced. The sodium silicate with the crystal water is sodium silicate nonahydrate.
The morphology of the carbon material is accurately controlled by adjusting the ratio of the template agent to the carbon source, and the nitrogen doping amount is accurately controlled by adjusting the ratio of the nitrogen source. Preferably, the mass ratio of the carbon source, the nitrogen source and the template is 1-10: 1-5: 10-30. Further preferably, the mass ratio of the carbon source, the nitrogen source, the template and the water is 1-10: 1-5: 10-30: 100.
Preferably, the temperature of the solvothermal reaction is 130-280 ℃, and more preferably 130-200 ℃. The solvothermal reaction time is 10-48 h.
Preferably, the preparation method of the noble metal platinum-based redox catalyst carrier further comprises washing the precipitate obtained by the solvothermal reaction, and then drying the washed precipitate. Preferably, the drying treatment performed after washing the precipitate is a vacuum drying treatment. The temperature of the vacuum drying is preferably 60 ℃.
Preferably, the temperature of the pyrolysis reaction is 700-1200 ℃. The time of the pyrolysis reaction is 2-5 h.
The noble metal platinum-based redox catalyst of the present invention can be prepared by a method comprising the steps of: the noble metal platinum-based redox catalyst carrier and the noble metal acetylacetone are uniformly mixed and then calcined in inert atmosphere, thus obtaining the catalyst. The catalyst prepared by the method can ensure that the noble metal is uniformly distributed on the surface of the carrier.
Preferably, the mass of the platinum acetylacetonate is calculated as noble metal platinum, and the mass ratio of the noble metal platinum to the carrier is 40: 60.
Preferably, the calcining temperature is 500 ℃, and the calcining time is 5 h.
Drawings
FIG. 1 is a scanning electron micrograph of a noble metal platinum-based redox catalyst prepared in example 1;
FIG. 2 is an X-ray diffraction chart of the noble metal platinum-based redox catalyst obtained in example 1.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
Example 1
The preparation method of the noble metal platinum-based redox catalyst carrier of the embodiment comprises the following steps:
1) uniformly mixing sodium chloride, glucose, urea and water in a mass ratio of 20:1:1:100 to obtain a clear and transparent solution, and removing water through freeze drying to obtain solid powder;
2) pyrolyzing the solid powder at 700 ℃ for 4h in nitrogen atmosphere, washing with deionized water for multiple times to remove a water-soluble sodium chloride template, and drying at 80 ℃ overnight to obtain a three-dimensional nitrogen-doped carbon nanosheet (3D-NPC for short);
3) uniformly dispersing the prepared 3D-NPC in ethanol (the mass ratio of the 3D-NPC to the ethanol is 1:50), adjusting the pH of the solution to 4 by using hydrochloric acid, and then adding tetrabutyl titanate (the addition amount is TiO)2Meter, 3D-NPC and TiO2The mass ratio of (1) to (5) at 160 ℃, then carrying out solvothermal reaction for 24 hours, washing the precipitate with deionized water and ethanol alternately for three times (namely deionized water washing-ethanol washing-deionized water washing), and carrying out vacuum drying at 60 ℃ to obtain TiO2the/NPC carrier.
The catalyst carrier prepared in this example was subjected to a scanning electron microscope test and an X-ray diffraction test, and the obtained scanning electron microscope image and the obtained X-ray diffraction image are shown in fig. 1 and fig. 2, respectively. As can be seen from fig. 1, the noble metal platinum-based redox catalyst carrier prepared in this embodiment exhibits a three-dimensional carbon network structure formed by the cross-linking of oxide-loaded carbon nanosheets under a scanning electron microscope, and the oxide metal particles are uniformly loaded on the carbon nanosheets without significant agglomeration.
As can be seen from FIG. 2, the composition and crystal structure of the prepared catalyst carrier are characterized, the broad peak at 26 degrees corresponds to the (002) crystal face of the graphitic carbon, and the peaks at the other positions and TiO2The characteristic peaks of (A) are identical (JCPDS No. 21-1272), which shows that TiO2Successful preparation of NPC support.
Example 2
The preparation method of the noble metal platinum-based redox catalyst carrier of the embodiment comprises the following steps:
1) uniformly mixing sodium silicate, sucrose, melamine and water in a mass ratio of 10:3:2:100 to obtain a clear and transparent solution, and removing water through freeze drying to obtain solid powder;
2) pyrolyzing the solid powder at 900 ℃ for 2h in a nitrogen atmosphere, washing with deionized water for multiple times to remove a water-soluble sodium chloride template, and then drying at 80 ℃ overnight to obtain a three-dimensional nitrogen-doped carbon nanosheet (3D-NPC for short);
3) uniformly dispersing the prepared 3D-NPC in isopropanol (the mass ratio of the 3D-NPC to the ethanol is 1:50), adjusting the pH of the solution to 3 by using hydrochloric acid, and then adding ammonium molybdate (the addition amount is MoO)3Meter, MoO3And 3D-NPC at a mass ratio of 30:70), then carrying out solvothermal reaction for 10h at 130 ℃, washing the precipitate for three times by using deionized water and ethanol alternately, and carrying out vacuum drying at 60 ℃ to obtain MoO3the/NPC carrier.
Example 3
The preparation method of the noble metal platinum-based redox catalyst carrier of the embodiment comprises the following steps:
1) uniformly mixing sodium silicate, sodium chloride, glucose, melamine and water in a mass ratio of 5:15:1:1:100 to obtain a clear and transparent solution, and removing water through freeze drying to obtain solid powder;
2) pyrolyzing the solid powder at 1000 ℃ for 5h in nitrogen atmosphere, washing with deionized water for multiple times to remove a water-soluble sodium chloride template, and then drying at 80 ℃ overnight to obtain a three-dimensional nitrogen-doped carbon nanosheet (3D-NPC for short);
3) the prepared 3D-NPC is uniformly dispersed in the normalIn propanol (3D-NPC and ethanol mass ratio of 1:50), the pH of the solution was adjusted to 6 using hydrochloric acid, and then ammonium tungstate (added in an amount of WO) was added3Meter, WO3And 3D-NPC at a mass ratio of 10:90), then carrying out solvothermal reaction for 48h at 190 ℃, washing the precipitate for three times by using deionized water and ethanol alternately, and carrying out vacuum drying at 60 ℃ to obtain WO3and/NPC, namely obtaining.
Example 4
The preparation method of the noble metal platinum-based redox catalyst carrier of the embodiment comprises the following steps:
1) uniformly mixing sodium silicate, sodium chloride, glucose, urea and water according to a mass ratio of 15:5:1:5:100 to obtain a clear transparent solution, and removing water through freeze drying to obtain solid powder;
2) pyrolyzing the solid powder at 1200 ℃ for 2 hours in a nitrogen atmosphere, washing with deionized water for multiple times to remove a water-soluble sodium chloride template, and then drying at 80 ℃ overnight to obtain a three-dimensional nitrogen-doped carbon nanosheet (3D-NPC for short);
3) the prepared NPC was uniformly dispersed in ethanol (3D-NPC to ethanol mass ratio 1:50), the pH of the solution was adjusted to 5 using hydrochloric acid, and then isopropyl titanate (added in an amount of TiO) was added2Meter, TiO2And 3D-NPC at a mass ratio of 20:80), then carrying out solvothermal reaction for 48h at 190 ℃, washing the precipitate for three times by using deionized water and ethanol alternately, and carrying out vacuum drying at 60 ℃ to obtain TiO2the/NPC carrier.
Example 5
The preparation method of the noble metal platinum-based redox catalyst carrier of the embodiment comprises the following steps:
1) uniformly mixing sodium silicate, sodium chloride, glucose, urea and water in a mass ratio of 9:6:5:1:100 to obtain a clear transparent solution, and removing water through freeze drying to obtain solid powder;
2) pyrolyzing the solid powder at 1200 ℃ for 2 hours in a nitrogen atmosphere, washing with deionized water for multiple times to remove a water-soluble sodium chloride template, and then drying at 80 ℃ overnight to obtain a three-dimensional nitrogen-doped carbon nanosheet (3D-NPC for short);
3) the prepared 3D-NPC areUniformly dispersing in ethanol (3D-NPC and ethanol at a mass ratio of 1:50), adjusting pH to 5 with hydrochloric acid, and adding isopropyl titanate (in an amount of TiO)2Meter, TiO2And 3D-NPC at a mass ratio of 15:85), performing solvothermal reaction at 190 ℃ for 48h, washing the precipitate with deionized water and ethanol alternately for three times, and drying at 60 ℃ in vacuum to obtain TiO2the/NPC carrier.
Example 6
The preparation method of the noble metal platinum-based redox catalyst carrier of the embodiment comprises the following steps:
1) uniformly mixing sodium silicate, sucrose, melamine and water in a mass ratio of 10:10:1:100 to obtain a clear and transparent solution, and removing water through freeze drying to obtain solid powder;
2) pyrolyzing the solid powder at 900 ℃ for 2 hours in a nitrogen atmosphere, washing with deionized water for multiple times to remove a water-soluble sodium chloride template, and then drying at 80 ℃ overnight to obtain a three-dimensional nitrogen-doped carbon nanosheet (3D-NPC for short);
3) uniformly dispersing the prepared 3D-NPC in isopropanol (the mass ratio of the 3D-NPC to the ethanol is 1:50), adjusting the pH of the solution to 4 by using hydrochloric acid, and then adding ammonium molybdate (the addition amount is MoO)3Meter, MoO3And 3D-NPC at a mass ratio of 30:70), then carrying out solvothermal reaction for 10h at 130 ℃, washing the precipitate for three times by using deionized water and ethanol alternately, and carrying out vacuum drying at 60 ℃ to obtain MoO3the/NPC carrier.
Example 7
The preparation method of the noble metal platinum-based redox catalyst carrier of the embodiment comprises the following steps:
1) uniformly mixing sodium silicate, sucrose, melamine and water in a mass ratio of 30:1:1:100 to obtain a clear and transparent solution, and removing water through freeze drying to obtain solid powder;
2) pyrolyzing the solid powder at 900 ℃ for 2 hours in a nitrogen atmosphere, washing with deionized water for multiple times to remove a water-soluble sodium chloride template, and then drying at 80 ℃ overnight to obtain a three-dimensional nitrogen-doped carbon nanosheet (3D-NPC for short);
3) the prepared 3D-NPC is uniformly dispersed in isopropanol (the mass ratio of 3D-NPC to ethanol is 1:50), the pH of the solution is adjusted to 3 by using hydrochloric acid, and then tetraethyl titanate (the addition amount is TiO)2Meter, TiO2And 3D-NPC at a mass ratio of 10:90), performing solvothermal reaction for 10h at 160 ℃, alternately washing the precipitate with deionized water and ethanol for three times, and performing vacuum drying at 60 ℃ to obtain TiO2the/NPC carrier.
Example 8
The preparation method of the noble metal platinum-based redox catalyst carrier of the embodiment comprises the following steps:
1) uniformly mixing sodium silicate, sodium chloride, glucose, urea and water in a mass ratio of 6:9:1:1:100 to obtain a clear transparent solution, and removing water through freeze drying to obtain solid powder;
2) pyrolyzing the solid powder at 1100 ℃ for 3 hours in nitrogen atmosphere, washing with deionized water for multiple times to remove a water-soluble sodium chloride template, and then drying at 80 ℃ overnight to obtain a three-dimensional nitrogen-doped carbon nanosheet (3D-NPC for short);
3) uniformly dispersing the prepared 3D-NPC in ethanol (the mass ratio of the 3D-NPC to the ethanol is 1:50), adjusting the pH of the solution to 5 by using hydrochloric acid, and then adding isopropyl titanate and ammonium molybdate (the addition amount of the isopropyl titanate is TiO)2Calculated by MoO, the adding amount of ammonium molybdate3Meter, TiO2And MoO3The ratio of the total mass of (3D-NPC) to the mass of (3D-NPC) is 10:90), then carrying out solvothermal reaction for 12h at 200 ℃, washing the precipitate for three times by using deionized water and ethanol alternately, and carrying out vacuum drying at 60 ℃ to obtain TiO2/MoO3the/NPC carrier.
In other embodiments of the noble metal platinum-based redox catalyst carrier of the present invention, the single metal oxide source in embodiments 1 to 8 may be replaced by a combination of two or more metal source oxides, for example, tetrabutyl titanate in embodiment 1 is replaced by a combination of ammonium tungstate and ammonium tungstate, or by a combination of isopropyl titanate and ammonium tungstate, or a combination of tetrabutyl titanate and ammonium molybdate, or a combination of tetrabutyl titanate, ammonium molybdate, and ammonium tungstate.
Examples of the experiments
In order to verify the performance of the noble metal platinum-based redox catalyst using the catalyst carrier of the present invention, the noble metal platinum-based redox catalysts were prepared according to the following methods, using the noble metal platinum-based redox catalyst carriers prepared in examples 1 to 8 as carriers, respectively: uniformly mixing a carrier and platinum acetylacetonate (the mass ratio of the platinum to the carrier is 40:60 in terms of the mass of the platinum), and calcining for 5 hours at 500 ℃ in a nitrogen atmosphere to obtain a 40 wt.% noble metal supported catalyst.
The electrical performance tests were performed on the noble metal platinum-based redox catalysts and the commercial platinum-carbon catalysts prepared using the supports of examples 1 to 8, respectively, and the electrical performance tests were performed using a conventional three-electrode device, in which the reference electrode was a reversible hydrogen electrode, the counter electrode was a platinum wire electrode, the working electrode was a glass disk electrode in which the catalyst was uniformly dispersed, and the electrolyte was 0.1mol/L of hcl o4And (3) solution.
The specific test steps are as follows:
1) making working electrodes
Placing a noble metal platinum-based redox catalyst, conductive carbon black, a Nafion solution (5 wt.%) and ethanol in a small bottle according to a mass ratio of 5:1:50:500, performing ultrasonic treatment for 1h to form uniform slurry, dripping the uniform slurry onto a glass disc electrode, and finally drying at normal temperature to obtain the working electrode.
2) Oxygen reduction Electrical Performance test
The oxygen reduction electrical performance test is carried out at room temperature, firstly, nitrogen is used for removing oxygen dissolved in the electrolyte, then cyclic voltammetry test is carried out at a scanning rate of 50mV/s, then, oxygen is introduced into the electrolyte to a saturated state, linear cyclic voltammetry test is carried out, and the stability of the catalyst is tested by a chronoamperometry.
The test results are shown in Table 1.
TABLE 1 carriers used in examples 1 to 8Bulk prepared noble metal platinum-based redox catalyst and commercial platinum-carbon catalyst in 0.1mol/L HClO4Half-wave potential of (1) and current retention rate after 20000s test
Figure BDA0002861453780000071
Figure BDA0002861453780000081
As can be seen from the test results in table 1, the platinum-based redox catalyst prepared by the preparation method of the present invention has significantly improved stability while maintaining high activity, as compared to commercial platinum-carbon catalysts.

Claims (10)

1. A preparation method of a noble metal platinum-based redox catalyst carrier is characterized by comprising the following steps: the method comprises the following steps: carrying out solvothermal reaction on nitrogen-doped porous carbon and a metal oxide source under an acidic condition; the metal oxide source is one or any combination of a titanium oxide source, a molybdenum oxide source and a tungsten oxide source.
2. The method for producing a noble metal platinum-based redox catalyst carrier according to claim 1, characterized in that: the mass of the metal oxide source is calculated by the mass of the metal oxide formed by the solvothermal reaction of the metal oxide source, and the mass ratio of the metal oxide to the nitrogen-doped porous carbon is 5-30: 70-95.
3. The method for producing a noble metal platinum-based redox catalyst carrier according to claim 1 or 2, characterized in that: the nitrogen-doped porous carbon is prepared by the following steps: and (2) uniformly dispersing the carbon source, the nitrogen source and the template agent in water, removing water, performing pyrolysis reaction in an inert atmosphere, washing away the template agent, and drying to obtain the carbon-based composite material.
4. The method of producing a noble metal platinum-based redox catalyst carrier according to claim 3, characterized in that: the mass ratio of the carbon source, the nitrogen source and the template agent is 1-10: 1-5: 10-30.
5. The method of producing a noble metal platinum-based redox catalyst carrier according to claim 4, characterized in that: the carbon source is selected from one or any combination of glucose and sucrose; the nitrogen source is selected from one or any combination of urea and melamine.
6. The method of producing a noble metal platinum-based redox catalyst carrier according to claim 3, characterized in that: the temperature of the pyrolysis reaction is 700-1200 ℃, and the time is 2-5 h.
7. The method of producing a noble metal platinum-based redox catalyst carrier according to claim 3, characterized in that: the water removal treatment is freeze drying.
8. The method for producing a noble metal platinum-based redox catalyst carrier according to claim 1 or 2, characterized in that: the pH of the acidic condition is 3-6.
9. The method for producing a noble metal platinum-based redox catalyst carrier according to claim 1 or 2, characterized in that: the temperature of the solvothermal reaction is 130-280 ℃, and the time is 10-48 h.
10. The method for producing a noble metal platinum-based redox catalyst carrier according to claim 1 or 2, characterized in that: the method also comprises the steps of washing the precipitate obtained by the solvothermal reaction and then drying.
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CN115367745A (en) * 2021-05-19 2022-11-22 北京化工大学 Tungsten-containing substance hybrid and nitrogen-doped porous carbon material and preparation method thereof

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