CN116404182B - Low-platinum catalyst, preparation method thereof and application thereof in fuel cell - Google Patents

Low-platinum catalyst, preparation method thereof and application thereof in fuel cell Download PDF

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CN116404182B
CN116404182B CN202310329149.3A CN202310329149A CN116404182B CN 116404182 B CN116404182 B CN 116404182B CN 202310329149 A CN202310329149 A CN 202310329149A CN 116404182 B CN116404182 B CN 116404182B
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solid powder
platinum
carbon
grinding
low
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CN116404182A (en
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吴爱明
朱凤鹃
吴若飞
郑文
陈伟
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Shanghai Tang Feng Energy Technology Co ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • 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 application provides a low-platinum catalyst, a preparation method and application thereof, and relates to the technical field of fuel cells. Dispersing a carbon carrier in absolute ethyl alcohol, adding a transition metal precursor, continuously stirring until the transition metal precursor is completely dissolved, heating and adjusting the pH value, continuously reacting, cleaning, filtering, drying and grinding to obtain first solid powder; the first solid powder is placed in an ammonia gas atmosphere for treatment to obtain carbon-supported metal nitride; dispersing the carbon-supported metal nitride in deionized water in which a noble metal precursor is dissolved, introducing a carbon monoxide atmosphere, reacting, cleaning, filtering, drying and grinding to obtain second solid powder; dispersing the second solid powder in a dilute sulfuric acid solution, introducing hydrogen, introducing argon, adding a platinum precursor, reducing by adsorbing hydrogen on the surface, cleaning, filtering, drying and grinding to obtain third solid powder; and the third solid powder is placed in a reducing atmosphere for treatment to obtain the low-platinum catalyst, so that the activity and stability of the catalyst are improved.

Description

Low-platinum catalyst, preparation method thereof and application thereof in fuel cell
Technical Field
The application relates to the technical field of fuel cells and nano materials, in particular to a low-platinum catalyst, a preparation method thereof and application thereof in fuel cells.
Background
The fuel cell converts the Gibbs free energy in the chemical energy of the fuel into electric energy through electrochemical reaction, and is not limited by the Carnot cycle effect, so that the conversion efficiency is higher; in addition, since it uses fuel and oxygen as raw materials, there is no mechanical transmission member, so that the discharged harmful gas is very little, and the service life is long, and these advantages make the fuel cell considered as a very promising energy power apparatus. The fuel cell catalyst is directly related to the performance and service life of the fuel cell stack, and the raw materials of platinum and platinum carbon particles are high in price, so that the catalyst becomes one of the most costly components in the fuel cell core component stack. Therefore, it is important to develop a high activity and high stability low platinum catalyst to solve the above problems.
Disclosure of Invention
In view of this, the embodiments of the present disclosure provide a low-platinum catalyst, a preparation method thereof, and an application in a fuel cell, which improve the activity and durability of the catalyst, so that the overall stability of the catalyst is higher.
The embodiment of the specification provides the following technical scheme:
in one aspect, a method for preparing a low platinum catalyst is provided, comprising:
dispersing a carbon carrier in absolute ethyl alcohol, adding a transition metal precursor, continuously stirring until the transition metal precursor is completely dissolved, heating and adjusting the pH value, continuously reacting, cleaning, filtering, drying and grinding to obtain first solid powder;
the first solid powder is placed in an ammonia gas atmosphere for treatment to obtain carbon-supported metal nitride;
dispersing the carbon-supported metal nitride in deionized water in which a noble metal precursor is dissolved, introducing a carbon monoxide atmosphere, reacting, cleaning, filtering, drying and grinding to obtain second solid powder;
dispersing the second solid powder in a dilute sulfuric acid solution, introducing hydrogen, introducing argon, adding a platinum precursor, reducing by adsorbing hydrogen on the surface, cleaning, filtering, drying and grinding to obtain third solid powder;
and (3) placing the third solid powder in a reducing atmosphere for treatment to obtain the low-platinum catalyst.
In some embodiments, dispersing the carbon carrier in absolute ethanol for 30-60 min, adding the transition metal precursor, continuously stirring for 10-30 min until the transition metal precursor is completely dissolved, then raising the temperature to 60 ℃, adjusting the pH value to 12-14 by using sodium hydroxide ethanol solution, continuously reacting for 5-12 h, washing, filtering, drying and grinding to obtain the first solid powder.
In some embodiments, the molar concentration of the sodium hydroxide ethanol solution is 1mol/L.
In some embodiments, the first solid powder is subjected to an ammonia atmosphere and a temperature of 400 ℃ to 600 ℃ for 1 hour to 3 hours to obtain the carbon-supported metal nitride.
In some embodiments, the carbon-supported metal nitride is dispersed in deionized water in which the noble metal precursor is dissolved, and carbon monoxide atmosphere is introduced, and the mixture is reacted at 25 ℃ for 3 to 8 hours, and the mixture is washed, filtered, dried and ground to obtain second solid powder.
In some embodiments, dispersing the second solid powder in a dilute sulfuric acid solution, introducing hydrogen for 1-5 hours, and then introducing argon; and then adding a platinum precursor solution, reducing platinum by adsorbing hydrogen on the surface and depositing the platinum on the surface, cleaning, filtering, drying and grinding to obtain third solid powder.
In some embodiments, the third solid powder is placed in hydrogen or hydrogen-argon mixture and treated for 1-3 hours at 300-500 ℃ to obtain the core-shell structured platinum-based catalyst.
In some embodiments, the carbon support has a solids content of 0.01g/mL to 0.1g/mL dispersed in absolute ethanol.
In some embodiments, the transition metal precursor is at least one of a chloride, nitrate, sulfate, acetate of a predetermined transition metal, including at least one of Fe, co, ni, nb, ti, mo.
In some embodiments, the noble metal precursor comprises at least one of palladium chloride, palladium chloride acid, sodium palladium chloride, palladium nitrate, chloroauric acid, gold chloride, ruthenium chloride, or a combination thereof.
In some embodiments, the concentration of the dilute sulfuric acid is between 0.1mol/L and 1mol/L.
In some embodiments, the platinum precursor comprises at least one or a combination of several of chloroplatinic acid, potassium chloroplatinate, ammonium chloroplatinate.
In some embodiments, the mass ratio of platinum to the second solid powder in the added platinum precursor is 1: 20-1: 2.
in some embodiments, the first solid powder comprises at least one of the following precipitates: co (Co) 3 O 4 /C、NiO 2 /C、NbO 2 /C、TiO 2 C and MoO 3 /C。
In some embodiments, the second solid powder comprises at least one of the following precipitates: pd@CoN/C, pd@CoN/C, pd/NiN/C, pd/NbN/C, pd/TiN/C, pd/MoN/C.
In some embodiments, the third solid powder comprises at least one of the following precipitates: pt@Pd@CoN/C, pt@Pd/NiN/C, pt@Pd/NbN/C, pt@Pd/TiN/C, and Pt@Pd/MoN/C.
In some embodiments, a core-shell structure for preparing a low platinum catalyst includes a nitride core in an inner core layer, a palladium intermediate layer in an intermediate layer, and a platinum shell outer layer in an outer layer.
In some embodiments, the low platinum catalyst is prepared with a nanoparticle size of 5nm to 10nm, wherein the inner core diameter size is 2nm to 5nm, the intermediate layer radial thickness is 2nm to 3nm, and the outer layer radial thickness is 0.5nm to 1nm.
In another aspect, a low platinum catalyst prepared by the method for preparing a low platinum catalyst according to any of the above embodiments is provided.
In yet another aspect, there is provided a use of a low platinum catalyst in a fuel cell, the low platinum catalyst according to any of the above embodiments being used in the preparation of a fuel cell.
Compared with the prior art, the beneficial effects that above-mentioned at least one technical scheme that this description embodiment adopted can reach include at least:
the conductivity of the carrier can be improved by oxidative nitridation to optimize the performance of the catalyst; meanwhile, the middle layer is designed to separate the nitride inner core from the outer layer Pt shell, so that the dissolution and oxidation of the inner core under the acidic condition can be reduced, and the stability of the catalyst with the core-shell structure is improved; meanwhile, the design of the middle layer is beneficial to the uniform distribution of the outer layer Pt shell, so that the agglomeration of Pt per se is reduced, and the utilization rate of the catalyst can be improved; and the reduction of defects of the outer layer Pt shell is facilitated by heat treatment, so that the activity and durability of the catalyst are further improved, and the overall stability of the catalyst is higher.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of a core-shell structure of a low-platinum catalyst according to an embodiment of the present application.
Detailed Description
Other advantages and effects of the present application will become apparent to those skilled in the art from the present disclosure, when the following description of the embodiments is taken in conjunction with the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. The present application may be embodied or carried out in other specific embodiments, and the details of the present application may be modified or changed from various points of view and applications without departing from the spirit of the present application. It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
It is noted that various aspects of the embodiments are described below within the scope of the following claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the present application, one skilled in the art will appreciate that one aspect described herein may be implemented independently of any other aspect, and that two or more of these aspects may be combined in various ways. For example, apparatus may be implemented and/or methods practiced using any number and aspects set forth herein. In addition, such apparatus may be implemented and/or such methods practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
It should also be noted that the illustrations provided in the following embodiments merely illustrate the basic concepts of the application by way of illustration, and only the components related to the application are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of the components in actual implementation may be arbitrarily changed, and the layout of the components may be more complicated. In addition, in the following description, specific details are provided in order to provide a thorough understanding of the examples. However, it will be understood by those skilled in the art that the present invention may be practiced without these specific details.
The preparation method of the low-platinum catalyst provided by the embodiment of the application comprises the following steps:
dispersing a carbon carrier in absolute ethyl alcohol, adding a transition metal precursor, continuously stirring until the transition metal precursor is completely dissolved, heating and adjusting the pH value, continuously reacting, cleaning, filtering, drying and grinding to obtain first solid powder;
step 2, placing the first solid powder in an ammonia gas atmosphere for treatment to obtain carbon-supported metal nitride;
step 3, dispersing the carbon-carried metal nitride in deionized water in which a noble metal precursor is dissolved, introducing carbon monoxide atmosphere, reacting, cleaning, filtering, drying and grinding to obtain second solid powder;
step 4, dispersing the second solid powder in a dilute sulfuric acid solution, introducing hydrogen, introducing argon, adding a platinum precursor, reducing by adsorbing hydrogen on the surface, cleaning, filtering, drying and grinding to obtain third solid powder;
and 5, placing the third solid powder in a reducing atmosphere for treatment to obtain the low-platinum catalyst.
In some embodiments, step 1 may be implemented as follows: dispersing the carbon by ultrasonic for 30 to 60 minutesDispersing the carrier in absolute ethyl alcohol, adding a transition metal precursor, continuously stirring for 10-30 min until the transition metal precursor is completely dissolved, then raising the temperature to 60 ℃, regulating the pH value to 12-14 by using a sodium hydroxide ethanol solution, continuously reacting for 5-12 h, cleaning, filtering, drying and grinding to obtain first solid powder. In some embodiments, the molar concentration of the sodium hydroxide ethanol solution is 1mol/L. In some embodiments, the carbon support has a solids content of 0.01g/mL to 0.1g/mL dispersed in absolute ethanol. In some embodiments, the transition metal precursor is at least one of a chloride, nitrate, sulfate, acetate of a predetermined transition metal, including at least one of Fe, co, ni, nb, ti, mo. In some embodiments, the first solid powder comprises at least one of the following precipitates: co (Co) 3 O 4 /C、NiO 2 /C、NbO 2 /C、TiO 2 C and MoO 3 /C。
In some embodiments, step 2 may be implemented as follows: and (3) placing the first solid powder in an ammonia gas atmosphere and treating for 1-3 hours at the temperature of 400-600 ℃ to obtain the carbon-supported metal nitride.
In some embodiments, step 3 may be implemented as follows: dispersing the carbon-supported metal nitride in deionized water in which a noble metal precursor is dissolved, introducing carbon monoxide atmosphere, reacting for 3-8 h at 25 ℃ (or other room temperature conditions), cleaning, filtering, drying and grinding to obtain second solid powder. In some embodiments, the noble metal precursor comprises at least one of palladium chloride, palladium chloride acid, sodium palladium chloride, palladium nitrate, chloroauric acid, gold chloride, ruthenium chloride, or a combination thereof. In some embodiments, the second solid powder comprises at least one of the following precipitates: pd@CoN/C, pd@CoN/C, pd/NiN/C, pd/NbN/C, pd/TiN/C, pd/MoN/C. It should be noted that in the examples of the present specification @ means that the former element substance is coated on the latter element substance, for example, pd @ CoN means that Pd is coated on the surface of CoN, i.e., pd @ CoN/C precipitate, pd is coated on the surface of CoN.
In some embodiments, step 4 may be implemented as follows: dispersing the second solid powder in a dilute sulfuric acid solution, and introducing hydrogen for 1-5 h, and then introducing argon; and then adding a platinum precursor solution, reducing platinum by adsorbing hydrogen on the surface and depositing the platinum on the surface, cleaning, filtering, drying and grinding to obtain third solid powder. In some embodiments, the concentration of the dilute sulfuric acid is between 0.1mol/L and 1mol/L. In some embodiments, the platinum precursor comprises at least one or a combination of several of chloroplatinic acid, potassium chloroplatinate, ammonium chloroplatinate. In some embodiments, the mass ratio of platinum to the second solid powder in the added platinum precursor is 1: 20-1: 2. in some embodiments, the third solid powder comprises at least one of the following precipitates: pt@Pd@CoN/C, pt@Pd/NiN/C, pt@Pd/NbN/C, pt@Pd/TiN/C, and Pt@Pd/MoN/C.
In some embodiments, step 5 may be implemented as follows: and (3) placing the third solid powder in hydrogen or hydrogen-argon mixed gas and treating for 1-3 hours at the temperature of 300-500 ℃ to obtain the core-shell structured platinum-based catalyst. In some embodiments, as shown in fig. 1, the core-shell structure for preparing the low-platinum catalyst includes a nitride core 11 at the core layer, a palladium intermediate layer 12 at the intermediate layer, and a platinum shell outer layer 13 at the outer layer. In some embodiments, the low platinum catalyst is prepared with a nanoparticle size of 5nm to 10nm, wherein the inner core diameter size is 2nm to 5nm, the intermediate layer radial thickness is 2nm to 3nm, and the outer layer radial thickness is 0.5nm to 1nm.
Some embodiments of the present application also provide a low-platinum catalyst prepared by the method for preparing a low-platinum catalyst according to any one of the above embodiments.
Some embodiments of the present application also provide an application of the low-platinum catalyst in a fuel cell, and the low-platinum catalyst according to any one of the embodiments above is applied to the preparation of the fuel cell.
The low platinum catalyst, the preparation method thereof and the application thereof in the fuel cell provided in the embodiments of the present application are further described below with reference to specific examples.
Example 1
Step 1, dispersing 5g of carbon powder in 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, and adding 14.75g of CoCl 2 ˙6H 2 O, continue stirring 10min until cobalt salt is completely dissolved; raising the temperature to 60 ℃, regulating the pH to 12 by using 1mol/L NaOH ethanol solution, continuing to react for 5 hours, cleaning, filtering, drying and grinding to obtain first solid powder;
step 2, the first solid powder (carbon-supported cobalt hydroxide, co (OH) 2 and/C) placing the mixture in a tubular furnace and treating the mixture for 1h at 400 ℃ in an ammonia atmosphere to obtain cobalt carbonitride;
step 3, dispersing 5g of cobalt carbonitride in an aqueous solution in which chloropalladate is dissolved, introducing CO atmosphere, reacting for 3 hours at room temperature, cleaning, filtering, drying and grinding to obtain second solid powder;
step 4, dispersing the second solid powder in 0.5mol/L dilute sulfuric acid solution, introducing hydrogen for 1h, and then introducing argon; then adding chloroplatinic acid solution (wherein, platinum and Co (OH) 2 The mass ratio of/C is 1:10 Reducing active hydrogen atoms obtained by Pd surface adsorption and hydrogen dissociation for 2 hours to obtain third solid powder;
and 5, placing the third solid powder in a hydrogen-argon mixed gas and treating for 1h at the temperature of 300 ℃ to obtain the core-shell structured platinum-based catalyst.
The prepared catalyst comprises a core layer (cobalt nitride core), an intermediate layer (Pd intermediate layer) and a platinum shell outer layer, and is loaded on a carbon carrier (Pt@Pd@CoN/C), and the size of nano particles with a core-shell structure is 5nm, so that the catalyst is used for preparing a fuel cell.
Example 2
Step 1, dispersing 5g of carbon powder in 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 40min, and adding 19.81g of FeCl 2 ˙4H 2 O, stirring for 30min until cobalt salt is completely dissolved; raising the temperature to 60 ℃, regulating the pH to 13 by using 1mol/L NaOH ethanol solution, continuing to react for 10 hours, cleaning, filtering, drying and grinding to obtain first solid powder;
step 2, the first solid powder (carbon-supported ferric hydroxide, fe (OH)) 2 and/C) placing the mixture in a tubular furnace and treating the mixture for 3 hours at the temperature of 500 ℃ in an ammonia atmosphere to obtain carbon-supported iron nitride;
step 3, dispersing 5g of carbon-supported iron nitride in an aqueous solution in which chloropalladate is dissolved, introducing CO atmosphere, reacting for 5 hours at room temperature, cleaning, filtering, drying and grinding to obtain second solid powder;
step 4, dispersing the second solid powder in 0.5mol/L dilute sulfuric acid solution, introducing hydrogen for 2 hours, and then introducing argon; then adding chloroplatinic acid solution (wherein, platinum and Fe (OH) 2 The mass ratio of/C is 1:10 Reducing active hydrogen atoms obtained by Pd surface adsorption and hydrogen dissociation for 2 hours to obtain third solid powder;
and 5, placing the third solid powder in hydrogen gas at 400 ℃ for 2 hours to obtain the core-shell structured platinum-based catalyst.
The prepared catalyst comprises an inner core layer (iron nitride inner core), an intermediate layer (Pd intermediate layer) and a platinum shell outer layer, and is loaded on a carbon carrier (Pt@Pd@FeN/C), and the size of nano particles with a core-shell structure is 6nm, so that the catalyst is used for preparing a fuel cell.
Example 3
Step 1, dispersing 5g of carbon powder in 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 60min, and adding 27.01g of NbCl 5 Stirring is continued for 30min until the cobalt salt is completely dissolved; raising the temperature to 60 ℃, regulating the pH to 13 by using 1mol/L NaOH ethanol solution, continuing to react for 8 hours, washing, filtering, drying and grinding to obtain first solid powder (carbon-supported niobium hydroxide, nb (OH)) 5 /C)；
Step 2, the first solid powder (carbon-supported niobium hydroxide, nb (OH)) 5 and/C) placing the mixture in a tube furnace and treating the mixture for 3 hours at 600 ℃ in an ammonia atmosphere to obtain niobium carbonitride;
step 3, dispersing 5g of niobium carbonitride in an aqueous solution in which chloropalladate is dissolved, introducing CO atmosphere, reacting for 5 hours at room temperature, cleaning, filtering, drying and grinding to obtain second solid powder;
step 4, dispersing the second solid powder in 0.5mol/L dilute sulfuric acid solution, introducing hydrogen for 3 hours, and then introducing argon; then adding chloroplatinic acid solution (wherein, platinum and Nb (OH) 5 The mass ratio of/C is 1:10 Reducing active hydrogen atoms obtained by adsorbing and dissociating hydrogen on the Pd surface for 2 hours to obtain third solid powder;
and 5, placing the third solid powder in a hydrogen-argon mixed gas and treating for 3 hours at the temperature of 300 ℃ to obtain the core-shell structured platinum-based catalyst.
The prepared catalyst comprises a core layer (niobium nitride inner layer), an intermediate layer (Pd intermediate layer) and a platinum shell outer layer, and is loaded on a carbon carrier (Pt@Pd@NbN/C), and the size of nano particles with a core-shell structure is 6.5nm, so that the catalyst is used for preparing a fuel cell.
Example 4
Step 1, dispersing 5g of carbon powder in 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, and adding 14.98g of NiCl 2 ˙6H 2 O, stirring for 30min until cobalt salt is completely dissolved; raising the temperature to 60 ℃, regulating the pH to 13 by using 1mol/L NaOH ethanol solution, continuing to react for 12 hours, washing, filtering, drying and grinding to obtain first solid powder (nickel hydroxide loaded on carbon, ni (OH) 2 /C)；
Step 2, the first solid powder (carbon-supported nickel hydroxide, ni (OH) 2 and/C) placing the nickel-carbon-loaded nickel-carbon nitride into a tubular furnace and treating the nickel-carbon-loaded nickel-carbon nitride for 3 hours at the temperature of 500 ℃ in an ammonia atmosphere;
step 3, dispersing 5g of nickel carbonitride in an aqueous solution in which chloropalladate is dissolved, introducing CO atmosphere, reacting for 6 hours at room temperature, cleaning, filtering, drying and grinding to obtain second solid powder;
step 4, dispersing the second solid powder in 0.5mol/L dilute sulfuric acid solution, introducing hydrogen for 5 hours, and then introducing argon; then, a chloroplatinic acid solution (wherein platinum and Ni (OH) are added) 2 The mass ratio of/C is 1:10 Reducing active hydrogen atoms obtained by Pd surface adsorption and hydrogen dissociation for 2 hours to obtain third solid powder;
and 5, placing the third solid powder in hydrogen at 500 ℃ for 3 hours to obtain the core-shell structured platinum-based catalyst.
The prepared catalyst comprises a core layer (nickel nitride core), an intermediate layer (Pd intermediate layer) and a platinum shell outer layer, and is loaded on a carbon carrier (Pt@Pd@NiN/C), and the size of nano particles with a core-shell structure is 6nm, so that the catalyst is used for preparing a fuel cell.
Example 5
Step 1, dispersing 5g of carbon powder in 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, and adding 18.62g of MoCl 5 Stirring is continued for 20min until the cobalt salt is completely dissolved; raising the temperature to 60 ℃, regulating the pH to 13 by using 1mol/L NaOH ethanol solution, continuing to react for 10 hours, cleaning, filtering, drying and grinding to obtain first solid powder (carbon-loaded molybdenum hydroxide, mo (OH)) 2 /C)；
Step 2, the first solid powder (carbon-supported molybdenum hydroxide, mo (OH)) 2 and/C) placing the mixture in a tubular furnace and treating the mixture for 3 hours at the temperature of 300 ℃ in an ammonia atmosphere to obtain molybdenum carbonitride;
step 3, dispersing 5g of molybdenum carbonitride in an aqueous solution in which chloropalladate is dissolved, introducing CO atmosphere, reacting for 8 hours at room temperature, cleaning, filtering, drying and grinding to obtain second solid powder;
step 4, dispersing the second solid powder in 0.5mol/L dilute sulfuric acid solution, introducing hydrogen for 2 hours, and then introducing argon; then adding chloroplatinic acid solution (wherein, platinum and Mo (OH) 2 The mass ratio of/C is 1:10 Reducing active hydrogen atoms obtained by adsorbing and dissociating hydrogen on the Pd surface for 2 hours to obtain third solid powder;
and 5, placing the third solid powder in a hydrogen-argon mixed gas at 400 ℃ for 3 hours to obtain the core-shell structured platinum-based catalyst.
The prepared catalyst comprises a core layer (molybdenum nitride core layer), an intermediate layer (Pd intermediate layer) and a platinum shell outer layer, and is loaded on a carbon carrier (Pt@Pd@MoN/C), and the size of the nano particles with the core-shell structure is 5nm, so that the catalyst is used for preparing a fuel cell.
Example 6
Step 1, dispersing 5g of carbon powder in 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, and adding 18.97g of TiCl 4 Stirring is continued for 30min until the cobalt salt is completely dissolved; raising the temperature to 60 ℃, regulating the pH to 13 by using 1mol/L NaOH ethanol solution, continuing to react for 10 hours, cleaning, filtering, drying and grinding to obtain first solid powder (carbon-loaded titanium oxide, tiO) 2 /C)；
Step 2, the first solidPowder (carbon-supported titanium oxide, tiO) 2 and/C) placing the mixture in a tubular furnace and treating the mixture for 3 hours at the temperature of 300 ℃ in an ammonia atmosphere to obtain titanium carbonitride;
step 3, dispersing 5g of titanium carbonitride B in an aqueous solution in which chloropalladate is dissolved, introducing CO atmosphere, reacting for 5 hours at room temperature, cleaning, filtering, drying and grinding to obtain second solid powder;
step 4, dispersing the second solid powder in 0.5mol/L dilute sulfuric acid solution, introducing hydrogen for 2 hours, and then introducing argon; then adding chloroplatinic acid solution (wherein, platinum and TiO 2 The mass ratio of/C is 1:10 Reducing active hydrogen atoms obtained by Pd surface adsorption and hydrogen dissociation for 2 hours to obtain third solid powder;
and 5, placing the third solid powder in a hydrogen-argon mixed gas and treating for 3 hours at the temperature of 300 ℃ to obtain the core-shell structured platinum-based catalyst.
The prepared catalyst comprises a core layer (titanium nitride layer), an intermediate layer (Pd intermediate layer) and a platinum shell outer layer, and is loaded on a carbon carrier (Pt@Pd@TiN/C), and the size of nano particles with a core-shell structure is 6nm, so that the catalyst is used for preparing a fuel cell.
Comparative example 1
The difference from example 1 is that the treatment atmosphere in step 2 was argon, and the other steps and treatment conditions were identical.
The prepared catalyst comprises a core layer (cobalt oxide core), an intermediate layer (Pd middle) and a platinum shell outer layer, and is loaded on a carbon carrier, and the size of the core-shell structure nanoparticle is 12nm.
Comparative example 2
The difference from example 1 is only that the treatment temperature in step 5 was 100℃and the other steps and treatment conditions were identical.
The prepared catalyst comprises a core layer (cobalt nitride layer), an intermediate layer (Pd intermediate layer) and a platinum shell outer layer, and is loaded on a carbon carrier, the size of nano particles of a core-shell structure is 8nm, and the thickness of the platinum shell layer is thicker and uneven.
TABLE 1 results data reflecting activity and durability for the catalysts prepared in examples 1-6 and comparative examples
As is clear from table 1 above, the low-platinum catalysts prepared in examples 1 to 6 each exhibited higher catalyst activity and durability, and the catalyst performance was excellent, as compared with comparative examples 1 and 2.
In summary, the low-platinum catalyst, the preparation method thereof and the application scheme in the fuel cell provided by the embodiment of the application have at least the following beneficial effects:
the conductivity of the carrier can be improved by oxidative nitridation to optimize the performance of the catalyst; meanwhile, the middle layer is designed to separate the nitride inner core from the outer layer Pt shell, so that the dissolution and oxidation of the inner core under the acidic condition can be reduced, and the stability of the catalyst with the core-shell structure is improved; meanwhile, the design of the middle layer is beneficial to the uniform distribution of the outer layer Pt shell, so that the agglomeration of Pt per se is reduced, and the utilization rate of the catalyst can be improved; and the reduction of defects of the outer layer Pt shell is facilitated by heat treatment, so that the activity and durability of the catalyst are further improved, and the overall stability of the catalyst is higher.
In this specification, identical and similar parts of the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. Meanwhile, the specification uses specific words to describe the embodiments of the specification. Reference to "one embodiment," "an embodiment," and/or "some embodiments" means that a particular feature, structure, or characteristic is associated with at least one embodiment of the present description. Thus, it should be emphasized and should be appreciated that two or more references to "an embodiment" or "one embodiment" or "an alternative embodiment" in various positions in this specification are not necessarily referring to the same embodiment. Furthermore, certain features, structures, or characteristics of one or more embodiments of the present description may be combined as suitable.
Furthermore, the order in which the elements and sequences are processed, the use of numerical letters, or other designations in the description are not intended to limit the order in which the processes and methods of the description are performed unless explicitly recited in the claims. While certain presently useful inventive embodiments have been discussed in the foregoing disclosure, by way of various examples, it is to be understood that such details are merely illustrative and that the appended claims are not limited to the disclosed embodiments, but, on the contrary, are intended to cover all modifications and equivalent arrangements included within the spirit and scope of the embodiments of the present disclosure. For example, while the system components described above may be implemented by hardware devices, they may also be implemented solely by software solutions, such as installing the described system on an existing processing device or mobile device.
While the basic concepts have been described above, it will be apparent to those skilled in the art that the foregoing detailed disclosure is by way of example only and is not intended to be limiting. Although not explicitly described herein, various modifications, improvements, and adaptations to the present disclosure may occur to one skilled in the art. Such modifications, improvements, and modifications are intended to be suggested within this specification, and therefore, such modifications, improvements, and modifications are intended to be included within the spirit and scope of the exemplary embodiments of the present invention.

Claims (18)

1. A method for preparing a low platinum catalyst, comprising:
dispersing a carbon carrier in absolute ethyl alcohol, adding a transition metal precursor, continuously stirring until the transition metal precursor is completely dissolved, heating and adjusting the pH value, continuously reacting, cleaning, filtering, drying and grinding to obtain first solid powder;
the first solid powder is placed in an ammonia gas atmosphere for treatment to obtain carbon-supported metal nitride;
dispersing the carbon-supported metal nitride in deionized water in which a noble metal precursor is dissolved, introducing a carbon monoxide atmosphere, reacting, cleaning, filtering, drying and grinding to obtain second solid powder;
dispersing the second solid powder in a dilute sulfuric acid solution, introducing hydrogen, introducing argon, adding a platinum precursor, reducing by adsorbing hydrogen on the surface, cleaning, filtering, drying and grinding to obtain third solid powder;
placing the third solid powder in a reducing atmosphere for treatment to obtain a low-platinum catalyst; wherein the third solid powder comprises at least one of the following precipitates: the core-shell structure for preparing the low-platinum catalyst comprises a nitride inner core positioned in an inner core layer, a palladium middle layer positioned in an intermediate layer and a platinum shell outer layer positioned in an outer layer.
2. The preparation method according to claim 1, wherein the carbon carrier is dispersed in absolute ethanol by ultrasonic dispersion for 30-60 min, the transition metal precursor is added and stirring is continued for 10-30 min until the transition metal precursor is completely dissolved, then the temperature is raised to 60 ℃, the pH value is regulated to 12-14 by sodium hydroxide ethanol solution, the reaction is continued for 5-12 h, and the first solid powder is obtained by washing, filtering, drying and grinding.
3. The preparation method according to claim 2, wherein the molar concentration of the sodium hydroxide ethanol solution is 1mol/L.
4. The preparation method according to claim 1, wherein the first solid powder is subjected to an ammonia gas atmosphere at 400-600 ℃ for 1-3 hours to obtain the carbon-supported metal nitride.
5. The preparation method according to claim 1, wherein the carbon-supported metal nitride is dispersed in deionized water in which the noble metal precursor is dissolved, and carbon monoxide atmosphere is introduced, and the mixture is reacted at 25 ℃ for 3 to 8 hours, and the second solid powder is obtained by washing, filtering, drying and grinding.
6. The method of claim 1, wherein the second solid powder is dispersed in a dilute sulfuric acid solution, hydrogen is introduced for 1 to 5 hours, and then argon is introduced; and then adding a platinum precursor solution, reducing platinum by adsorbing hydrogen on the surface and depositing the platinum on the surface, cleaning, filtering, drying and grinding to obtain third solid powder.
7. The preparation method according to claim 1, wherein the third solid powder is placed in hydrogen or hydrogen-argon mixture and treated for 1-3 hours at 300-500 ℃ to obtain the core-shell platinum-based catalyst.
8. The method according to claim 1, wherein the carbon carrier has a solid content of 0.01g/mL to 0.1g/mL dispersed in absolute ethanol.
9. The method of claim 1, wherein the transition metal precursor is at least one of chloride, nitrate, sulfate, acetate of a predetermined transition metal, the predetermined transition metal comprising at least one of Fe, co, ni, nb, ti, mo.
10. The method according to claim 1, wherein the noble metal precursor comprises at least one or a combination of palladium chloride, palladium chloride acid, sodium chloropalladate, palladium nitrate, chloroauric acid, gold chloride, ruthenium chloride.
11. The process according to claim 1, wherein the concentration of the dilute sulfuric acid is 0.1mol/L to 1mol/L.
12. The method according to claim 1, wherein the platinum precursor comprises at least one or a combination of a plurality of chloroplatinic acid, potassium chloroplatinate, and ammonium chloroplatinate.
13. The method of claim 1, wherein the mass ratio of platinum to the second solid powder in the added platinum precursor is 1: 20-1: 2.
14. the method of claim 1, wherein the first solid powder comprises at least the following precipitatesOne or two of: co (Co) 3 O 4 /C、NiO 2 /C、NbO 2 /C、TiO 2 C and MoO 3 /C。
15. The method of claim 1, wherein the second solid powder comprises at least one of the following precipitates: pd@CoN/C, pd@CoN/C, pd/NiN/C, pd/NbN/C, pd/TiN/C, pd/MoN/C.
16. The preparation method according to claim 1, wherein the low-platinum catalyst is prepared in a nanoparticle size of 5nm to 10nm, wherein the diameter size of the inner core is 2nm to 5nm, the radial thickness of the intermediate layer is 2nm to 3nm, and the radial thickness of the outer layer is 0.5nm to 1nm.
17. A low-platinum catalyst characterized by being produced by the method for producing a low-platinum catalyst according to any one of claims 1 to 16.
18. Use of a low platinum catalyst in a fuel cell, characterized in that the low platinum catalyst according to claim 17 is used for the production of a fuel cell.
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Publication number Priority date Publication date Assignee Title
CN113600209A (en) * 2021-08-23 2021-11-05 西安交通大学 Method for preparing high-dispersion carbon-supported Pt-based ordered alloy catalyst and catalyst
CN114570357A (en) * 2020-12-02 2022-06-03 中国科学院大连化学物理研究所 Preparation method and application of Pd core @ Pt shell/C catalyst with core-shell structure
CN115799531A (en) * 2022-11-29 2023-03-14 中国科学院大连化学物理研究所 Non-noble metal nitrogen-carbon supported platinum alloy electrocatalyst for fuel cell and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114570357A (en) * 2020-12-02 2022-06-03 中国科学院大连化学物理研究所 Preparation method and application of Pd core @ Pt shell/C catalyst with core-shell structure
CN113600209A (en) * 2021-08-23 2021-11-05 西安交通大学 Method for preparing high-dispersion carbon-supported Pt-based ordered alloy catalyst and catalyst
CN115799531A (en) * 2022-11-29 2023-03-14 中国科学院大连化学物理研究所 Non-noble metal nitrogen-carbon supported platinum alloy electrocatalyst for fuel cell and preparation method and application thereof

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