CN114709438A - Platinum-based multi-element metal catalyst, and preparation method and application thereof - Google Patents
Platinum-based multi-element metal catalyst, and preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
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- 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
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- H01M2008/1095—Fuel cells with polymeric electrolytes
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Abstract
The invention provides a platinum-based multi-element metal catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving a platinum precursor, a transition metal precursor, a free radical quencher precursor and a carbon material in a solvent to form reaction slurry, carrying out reduction reaction on the reaction slurry under microwave irradiation to obtain a catalyst precursor, and then carrying out alloying treatment on the catalyst precursor to obtain the platinum-based multi-element metal catalyst. The platinum-based multi-element metal catalyst prepared by the preparation method provided by the invention can improve the oxygen reduction activity of the catalyst and the technical effect of improving the durability of a fuel cell while reducing the production cost of the catalyst by the interaction between the platinum transition metal alloy particles and the free radical quencher particles.
Description
Technical Field
The invention belongs to the technical field of new energy nano materials, and particularly relates to a platinum-based multi-element metal catalyst and a preparation method and application thereof.
Background
Proton exchange membrane fuel cells can convert chemical energy directly into electrical energy, wherein the anode undergoes a Hydrogen Oxidation Reaction (HOR) to produce hydrogen ions and electrons; the cathode generates Oxygen Reduction Reaction (ORR) to generate water, however, the ORR kinetic process is very slow, and a catalyst is required to reduce the reaction energy barrier and accelerate the reaction process, and the most commonly used catalyst is a platinum carbon catalyst with high electrochemical activity and stability, but due to the scarcity of platinum reserves, the cost of the catalyst is high, and the commercialization process of the fuel cell is influenced.
At present, the 3d group transition metal and platinum are adopted to form an alloy, and the Pt-M bond in the alloy can enhance the adsorbability of reactant oxygen, is beneficial to improving the reaction activity of the catalyst and reducing the platinum dosage, thereby reducing the catalyst cost. However, the transition metal element can generate more hydrogen peroxide intermediate products in the ORR process, form free radicals, attack organic functional groups in the proton exchange membrane, reduce the mechanical properties and proton conductivity of the proton exchange membrane, and cause the durability of the proton exchange membrane to be poor.
CN111129508A discloses a transition metal doped platinum-carbon catalyst, a preparation method and application thereof. The method comprises the following steps: mixing a carbon material, a precursor solution of platinum and a transition metal salt to obtain a mixed solution; mixing the obtained mixed solution with a reducing agent, separating and drying to obtain a precursor material; carrying out heat treatment on the obtained precursor material to obtain transition metal doped platinum-based nanoparticles; mixing the obtained transition metal doped platinum-based nanoparticles with a perfluorosulfonic acid solution, separating and drying to obtain the catalyst. The transition metal doped platinum-carbon catalyst forms a continuous proton conduction network by being coated by a perfluorosulfonic acid membrane, so that the current density is improved.
CN110265680A discloses a high-performance transition metal-containing catalyst, a preparation method and an application thereof, which is characterized in that transition metal or oxide thereof is doped in a carbon material used as an electronic conductor, and then platinum nanowires are supported on the surface of the carbon material to form the high-performance platinum catalyst. The transition metal and the platinum in the transition metal-containing catalyst form a synergistic effect, so that the performance of the fuel cell is improved while the use amount of the platinum is reduced.
CN112825357A discloses a Pt-based multi-component transition metal alloy nano electrocatalyst, its preparation and application, the preparation method comprises: dispersing a conductive carbon carrier in a polyhydric alcohol solution, and adjusting the pH value of the solution; dissolving a platinum precursor and a transition metal precursor in the same polyol solution, and adjusting the pH value of the solution; uniformly mixing a polyalcohol solution of a platinum precursor and a transition metal precursor with a conductive carbon polyalcohol solution to obtain a powdery catalyst precursor; and heating and activating the powdery catalyst precursor in a reducing atmosphere to obtain the PtM/C alloy catalyst. The nano catalyst has high alloying degree and good catalytic activity.
The above documents all improve the platinum-carbon catalyst by doping transition metal, but do not effectively solve the problem that the transition metal generates hydrogen peroxide intermediate product in the oxygen reduction process, forms free radicals, attacks the proton exchange membrane, and causes the reduction of the service life of the fuel cell. Therefore, there is a need to develop a transition metal platinum-based catalyst capable of simultaneously improving the activity of a fuel cell catalyst and the durability of a fuel cell.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a platinum-based multi-element metal catalyst and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a platinum-based multi-element metal catalyst, the method comprising:
dissolving a platinum precursor, a transition metal precursor, a free radical quencher precursor and a carbon material in a solvent to form reaction slurry, carrying out reduction reaction on the reaction slurry under microwave irradiation to obtain a catalyst precursor, and then carrying out alloying treatment on the catalyst precursor to obtain the platinum-based multi-element metal catalyst.
The platinum-based multi-element metal catalyst prepared by the invention contains a carbon carrier, and platinum transition metal alloy particles and free radical quencher particles (cerium oxide or manganese oxide) which are loaded on the carbon carrier, wherein the platinum transition metal alloy particles can enhance the adsorbability to reactant oxygen and are beneficial to improving the reaction activity of the catalyst, and the free radical quencher particles can effectively relieve the damage of free radicals generated in the reaction process of transition metals to a proton exchange membrane, so that the reaction activity of the catalyst can be improved, the production cost of the catalyst is reduced, the service life of the proton exchange membrane is prolonged, and the durability of a fuel cell is further improved.
Meanwhile, the reaction slurry is reduced by adopting a reducing solvent under microwave irradiation, wherein the propagation rate of microwaves, namely electromagnetic waves, is the same as the light speed, and when the microwave, namely the electromagnetic waves, is used as heating energy, materials can generate heat effects through molecular polarization, friction, collision and the like in a very short time to reach the temperature required by the reaction, so that the temperature distribution of the materials is more uniform, the reduction reaction is more efficient, and the nano particles on a catalyst carrier are more uniformly distributed, thereby effectively solving the problems that the heat transfer rate is lower in the traditional heating mode, the temperature distribution of the reaction slurry is not uniform, and the performance of the catalyst is adversely affected.
In addition, under microwave irradiation, the platinum precursor and the transition metal precursor are subjected to reduction reaction to form platinum particles and transition metal particles respectively, and the radical quencher precursor is not reduced but exists in the form of oxide, so that the catalyst precursor obtained by the invention comprises a carbon material carrier, and platinum particles, transition metal particles and radical quencher particles (cerium oxide or manganese oxide) positioned on the carbon carrier.
The platinum-based multi-element metal catalyst prepared by the preparation method provided by the invention can improve the oxygen reduction activity of the catalyst and the technical effect of improving the durability of a fuel cell while reducing the production cost of the catalyst by the interaction between the platinum transition metal alloy particles and the free radical quencher particles.
As a preferred technical solution of the present invention, the preparation process of the reaction slurry comprises:
dissolving the platinum precursor, the transition metal precursor and the free radical quencher precursor in a solvent to form a mixed solution, and then adding the carbon material into the mixed solution for shearing and emulsifying to obtain the reaction slurry.
According to the invention, the platinum precursor, the transition metal precursor and the free radical quencher precursor are dissolved in the solvent to form a uniform mixed solution, and then the carbon material is added for shearing and emulsification, so that the dispersion uniformity of the platinum precursor, the transition metal precursor and the free radical quencher precursor on the carbon material is improved, and the interaction between the platinum transition metal alloy particles and the free radical quencher particles is exerted.
Preferably, a base is further added to the mixed solution.
The invention adds proper amount of alkali into the mixed solution, because the alkali can firstly form hydroxide with the platinum precursor and the transition metal precursor, and the hydroxide has lower oxidation-reduction potential, weaker oxidizability and easier reduction in a solvent system with weaker reducibility (such as an ethylene glycol system).
Preferably, the base comprises sodium hydroxide and/or potassium hydroxide.
In a preferred embodiment of the present invention, the molar ratio of the platinum precursor, the transition metal precursor, and the radical quencher precursor is 1 (0.1 to 1) (0.01 to 0.1), and may be, for example, 1:0.1:0.01, 1:0.2:0.02, 1:0.3:0.03, 1:0.4:0.04, 1:0.5:0.05, 1:0.6:0.06, 1:0.7:0.07, 1:0.8:0.08, 1:0.9:0.09, 1:1:0.1, or 1:0.4:0.06, but is not limited to the above-mentioned values, and other values not mentioned within the above-mentioned range are also applicable.
The invention limits the molar ratio of the platinum precursor to the transition metal precursor to the free radical quencher precursor to be 1 (0.1-1) to 0.01-0.1, because the working environment of the fuel cell is acidic, the transition metal is easy to dissolve and run off in the acidic environment, and thus the catalyst has poor chemical stability and short service life due to the overhigh content of the transition metal; and the content of the transition metal is too low, so that the effect of reducing the dosage of the catalyst platinum is not obvious. Meanwhile, the addition of the free radical quencher can sacrifice the performance of the catalyst to a certain extent to improve the service life of the proton exchange membrane, so the addition amount needs to take the performance of the catalyst and the performance of the proton exchange membrane into consideration.
Preferably, the platinum precursor includes any one of chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate, ammonium chloroplatinate, potassium chloroplatinate, sodium chloroplatinate, or platinum acetylacetonate, or a combination of at least two thereof.
Preferably, the transition metal precursor includes any one of a nitrate, a sulfate, an acetylacetonate, or a chloride of a transition metal or a combination of at least two thereof.
Preferably, the transition metal in the transition metal precursor includes any one of cobalt, nickel, iron, or copper.
Preferably, the radical quencher precursor comprises any one of cerium nitrate, manganese nitrate, cerium chloride or manganese chloride.
Preferably, the solvent comprises any one of ethanol, ethylene glycol or isopropanol or a combination of at least two thereof.
The solvents in the invention are all reducing solvents, so that the platinum precursor and the transition metal precursor can be reduced under microwave irradiation.
Preferably, the carbon material comprises an activated carbon material.
Preferably, the activated carbon material comprises any one of XC-72R, Ketjen black EC-300J, Ketjen black EC-600J, carbon nanotubes, nano graphite powder and graphene or a combination of at least two of the materials.
Preferably, the concentration of the carbon material in the solvent is 0.5 to 10mg/mL, and may be, for example, 0.5mg/mL, 1mg/mL, 2mg/mL, 3mg/mL, 4mg/mL, 5mg/mL, 6mg/mL, 7mg/mL, 8mg/mL, 9mg/mL, or 10mg/mL, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In a preferred embodiment of the present invention, the rotation speed of the shearing emulsification is 8000-13000 rpm/min, for example 8000rpm/min, 9000rpm/min, 10000rpm/min, 11000rpm/min, 12000rpm/min or 13000rpm/min, but the number is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the time for the shear emulsification is 0.5 to 6 hours, for example, 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction slurry has a pH of 10 to 13, for example 10, 10.5, 11, 11.5, 12, 12.5 or 13, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
The pH value of the reaction slurry is regulated to 10-13 by regulating the amount of alkali added into the mixed solution.
In a preferred embodiment of the present invention, the temperature of the microwave irradiation is 130 to 190 ℃, and may be, for example, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, or 190 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
The method limits the temperature of microwave irradiation to be 130-190 ℃, and when the temperature is lower than 130 ℃, the platinum precursor and the transition metal precursor can not be reduced, because the temperature is too low, the temperature required by the reduction reaction of the platinum precursor and the transition metal precursor can not be reached; when the temperature is higher than 190 ℃, the platinum particles and the transition metal particles generated by the reduction reaction are agglomerated, because the metal nanoparticles are agglomerated in a short time at an excessively high temperature, and the catalytic activity is reduced.
Preferably, the microwave irradiation time is 2-60 min, such as 2min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the listed values, and other values not listed in the range of the values are also applicable.
Preferably, after the microwave irradiation, filtering, washing and vacuum drying are sequentially performed to obtain the catalyst precursor.
Preferably, the end point of the filtration wash is the conductivity of the filtrate < 5. mu.S/cm, which may be, for example, 5. mu.S/cm, 4.5. mu.S/cm, 4. mu.S/cm, 3.5. mu.S/cm, 3. mu.S/cm, 2.5. mu.S/cm or 2. mu.S/cm, but is not limited to the values listed, and other values not listed in this range of values are equally applicable.
The invention limits the end point of filtering and washing to be that the conductivity of the filtrate is less than or equal to 5 mu S/cm, because ions in the metal precursor, such as chloride ions, nitrate radicals, sulfate radicals and the like, can be adsorbed on the active sites of the catalyst if not cleaned, and can shield the catalytic activity, so that the conductivity of the filtrate needs to be strictly controlled in the cleaning stage to judge that the ion content in the catalyst reaches the standard.
In a preferred embodiment of the present invention, the temperature of the alloying treatment is 500 to 1200 ℃, and may be, for example, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ or 1200 ℃, but the alloying treatment is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable.
The invention puts the catalyst precursor into a tube furnace for alloying treatment. In addition, during the alloying process, the platinum particles and the transition metal particles in the catalyst precursor form an alloy, and the alloying process does not affect the radical quencher particles, which are still in an oxidized state (cerium oxide or manganese oxide), because the alloying condition is that the melting points of the two materials are close, wherein the melting points of platinum and the transition metal (cobalt, nickel, iron or copper) are about 1500 ℃, the melting points are close, the melting point of cerium oxide is 2397 ℃, the melting point of manganese oxide is 535 ℃, the difference between the melting points of platinum and the transition metal is larger, and the alloy cannot be formed.
Preferably, the time of the alloying treatment is 0.5 to 12 hours, for example, 0.5 hour, 1 hour, 2 hours, 0.5 hour, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
Preferably, the alloying treatment is performed under a protective atmosphere.
Preferably, the protective atmosphere comprises nitrogen or argon.
As a preferable technical solution of the present invention, the preparation method comprises:
(1) dissolving a platinum precursor, a transition metal precursor and a free radical quencher precursor in a solvent according to a molar ratio of 1 (0.1-1): (0.01-0.1), adding alkali to form a mixed solution, then adding a carbon material into the mixed solution, and performing shearing emulsification for 0.5-6 h at a rotating speed of 8000-13000 rpm/min to obtain reaction slurry, wherein the concentration of the carbon material in the solvent is 0.5-10 mg/mL;
(2) carrying out reduction reaction on the reaction slurry obtained in the step (1) for 2-60 min at the microwave irradiation temperature of 130-190 ℃, then filtering and washing until the conductivity of the filtrate is less than or equal to 5 muS/cm, and then carrying out vacuum drying to obtain a catalyst precursor;
(3) and (3) under a protective atmosphere, carrying out alloying treatment on the catalyst precursor obtained in the step (2) at the temperature of 500-1200 ℃ for 0.5-12 h to obtain the platinum-based multi-element metal catalyst.
In a second aspect, the invention provides a platinum-based multi-element metal catalyst, which is prepared by the preparation method of the first aspect.
As a preferred embodiment of the present invention, the platinum-based multi-component metal catalyst includes a carbon support, platinum transition metal alloy particles, and radical quencher particles, and both the platinum transition metal alloy particles and the radical quencher particles are supported on the carbon support.
The radical quencher particles of the present invention include cerium oxide particles or manganese oxide particles.
Preferably, the mass fraction of the platinum transition metal alloy particles is 10 to 80 wt%, for example, 10 wt% or 10 wt%, based on 100 wt% of the mass fraction of the platinum-based multi-element metal catalyst, but is not limited to the recited values, and other non-recited values within the range are also applicable.
In a third aspect, the present invention provides a use of the platinum-based multimetallic catalyst of the second aspect for a proton exchange membrane fuel cell.
Compared with the prior art, the invention has the beneficial effects that:
the platinum-based multi-element metal catalyst prepared by the preparation method provided by the invention can improve the oxygen reduction activity of the catalyst and the technical effect of improving the durability of a fuel cell while reducing the production cost of the catalyst by the interaction between the platinum transition metal alloy particles and the free radical quencher particles.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a platinum-based multi-element metal catalyst, which comprises the following steps:
(1) dissolving 1mmol of chloroplatinic acid, 0.5mmol of cobalt chloride, 0.05mmol of cerium nitrate and 0.5mmol of potassium hydroxide in 50mL of ethylene glycol to form a mixed solution, then adding 223mg of Ketjen black EC-600J activated carbon powder into the mixed solution, and carrying out shearing emulsification at the rotating speed of 10000rpm/min for 2h to obtain reaction slurry, wherein the concentration of the Ketjen black EC-600J activated carbon powder in the ethylene glycol is 4.46 mg/mL;
(2) carrying out reduction reaction on the reaction slurry obtained in the step (1) for 10min at the microwave irradiation temperature of 150 ℃, then filtering and washing until the conductivity of the filtrate is less than or equal to 5 mu S/cm, and then carrying out vacuum drying to obtain a catalyst precursor;
(3) and (3) carrying out alloying treatment on the catalyst precursor obtained in the step (2) at the temperature of 800 ℃ for 5 hours in an argon atmosphere to obtain the platinum-based multi-element metal catalyst, wherein the mass fraction of platinum-cobalt alloy particles in the platinum-based multi-element metal catalyst is about 50 wt%.
Example 2
The embodiment provides a preparation method of a platinum-based multi-element metal catalyst, which comprises the following steps:
(1) dissolving 1mmol of sodium chloroplatinate, 0.1mmol of ferric nitrate, 0.01mmol of cerium nitrate and 1.8mmol of sodium hydroxide in 180mL of isopropanol to form a mixed solution, then adding 1800mg of XC-72R activated carbon powder into the mixed solution, and carrying out shearing emulsification for 6 hours at the rotating speed of 8000rpm/min to obtain reaction slurry, wherein the concentration of the XC-72R activated carbon powder in the isopropanol is 10 mg/mL;
(2) carrying out reduction reaction on the reaction slurry obtained in the step (1) for 60min at the microwave irradiation temperature of 130 ℃, then filtering and washing until the conductivity of the filtrate is less than or equal to 5 mu S/cm, and then carrying out vacuum drying to obtain a catalyst precursor;
(3) and (3) under the nitrogen atmosphere, carrying out alloying treatment on the catalyst precursor obtained in the step (2) at the temperature of 500 ℃ for 12 hours to obtain the platinum-based multi-element metal catalyst, wherein the mass fraction of platinum-iron alloy particles in the platinum-based multi-element metal catalyst is about 10 wt%.
Example 3
The embodiment provides a preparation method of a platinum-based multi-element metal catalyst, which comprises the following steps:
(1) dissolving 1mmol of potassium chloroplatinate, 1mmol of nickel acetylacetonate, 0.1mmol of manganese chloride and 1.27mmol of potassium hydroxide in 127mL of ethanol to form a mixed solution, then adding 63.5mg of Ketjen black EC-300J activated carbon powder into the mixed solution, and carrying out shearing emulsification for 0.5h at the rotating speed of 13000rpm/min to obtain reaction slurry, wherein the concentration of the Ketjen black EC-300J activated carbon powder in the ethanol is 0.5 mg/mL;
(2) carrying out reduction reaction on the reaction slurry obtained in the step (1) for 2min at the microwave irradiation temperature of 190 ℃, then filtering and washing until the conductivity of the filtrate is less than or equal to 5 mu S/cm, and then carrying out vacuum drying to obtain a catalyst precursor;
(3) and (3) alloying the catalyst precursor obtained in the step (2) at 1200 ℃ for 0.5h in an argon atmosphere to obtain the platinum-based multi-element metal catalyst, wherein the mass fraction of platinum-nickel alloy particles in the platinum-based multi-element metal catalyst is about 80 wt%.
Example 4
The embodiment provides a preparation method of a platinum-based multi-element metal catalyst, which comprises the following steps:
(1) dissolving 1mmol of ammonium chloroplatinate, 0.5mmol of copper sulfate, 0.05mmol of cerium nitrate and 0.5mmol of potassium hydroxide in 50mL of ethanol to form a mixed solution, then adding 223mg of carbon nanotube powder into the mixed solution, and performing shearing emulsification for 2 hours at the rotating speed of 10000rpm/min to obtain reaction slurry, wherein the concentration of the carbon nanotube powder in the ethanol is 4.46 mg/mL;
(2) carrying out reduction reaction on the reaction slurry obtained in the step (1) for 10min at the microwave irradiation temperature of 150 ℃, then filtering and washing until the conductivity of the filtrate is less than or equal to 5 mu S/cm, and then carrying out vacuum drying to obtain a catalyst precursor;
(3) and (3) carrying out alloying treatment on the catalyst precursor obtained in the step (2) at the temperature of 800 ℃ for 5 hours in an argon atmosphere to obtain the platinum-based multi-element metal catalyst, wherein the mass fraction of platinum-copper alloy particles in the platinum-based multi-element metal catalyst is about 48 wt%.
Example 5
The embodiment provides a preparation method of a platinum-based multi-element metal catalyst, which comprises the following steps:
(1) dissolving 1mmol of sodium chloroplatinite, 0.5mmol of cobalt chloride, 0.05mmol of cerium nitrate and 0.5mmol of potassium hydroxide in 50mL of ethylene glycol to form a mixed solution, then adding 223mg of carbon nanotube powder into the mixed solution, and carrying out shearing emulsification for 2 hours at the rotating speed of 10000rpm/min to obtain reaction slurry, wherein the concentration of the carbon nanotube powder in the ethylene glycol is 4.46 mg/mL;
(2) carrying out reduction reaction on the reaction slurry obtained in the step (1) for 10min at the microwave irradiation temperature of 150 ℃, then filtering and washing until the conductivity of the filtrate is less than or equal to 5 mu S/cm, and then carrying out vacuum drying to obtain a catalyst precursor;
(3) and (3) carrying out alloying treatment on the catalyst precursor obtained in the step (2) at the temperature of 800 ℃ for 5 hours in an argon atmosphere to obtain the platinum-based multi-element metal catalyst, wherein the mass fraction of platinum-cobalt alloy particles in the platinum-based multi-element metal catalyst is about 50 wt%.
Example 6
The embodiment provides a preparation method of a platinum-based multi-element metal catalyst, which comprises the following steps:
(1) dissolving 1mmol of potassium chloroplatinite, 0.5mmol of cobalt chloride, 0.05mmol of cerium nitrate and 0.5mmol of potassium hydroxide in 50mL of ethylene glycol to form a mixed solution, then adding 223mg of nano graphite powder into the mixed solution, and carrying out shearing emulsification for 2 hours at the rotating speed of 10000rpm/min to obtain reaction slurry, wherein the concentration of the nano graphite powder in the ethylene glycol is 4.46 mg/mL;
(2) carrying out reduction reaction on the reaction slurry obtained in the step (1) for 10min at the microwave irradiation temperature of 150 ℃, then filtering and washing until the conductivity of the filtrate is less than or equal to 5 mu S/cm, and then carrying out vacuum drying to obtain a catalyst precursor;
(3) and (3) carrying out alloying treatment on the catalyst precursor obtained in the step (2) at the temperature of 800 ℃ for 5 hours in an argon atmosphere to obtain the platinum-based multi-element metal catalyst, wherein the mass fraction of platinum-cobalt alloy particles in the platinum-based multi-element metal catalyst is about 50 wt%.
Example 7
The embodiment provides a preparation method of a platinum-based multi-element metal catalyst, which comprises the following steps:
(1) dissolving 1mmol of platinum acetylacetonate, 0.5mmol of cobalt chloride, 0.05mmol of cerium nitrate and 0.5mmol of potassium hydroxide in 50mL of ethylene glycol to form a mixed solution, then adding 223mg of graphene powder into the mixed solution, and carrying out shearing emulsification for 2 hours at the rotating speed of 10000rpm/min to obtain reaction slurry, wherein the concentration of the graphene powder in the ethylene glycol is 4.46 mg/mL;
(2) carrying out reduction reaction on the reaction slurry obtained in the step (1) for 10min at the microwave irradiation temperature of 150 ℃, then filtering and washing until the conductivity of the filtrate is less than or equal to 5 mu S/cm, and then carrying out vacuum drying to obtain a catalyst precursor;
(3) and (3) carrying out alloying treatment on the catalyst precursor obtained in the step (2) at the temperature of 800 ℃ for 5 hours in an argon atmosphere to obtain the platinum-based multi-element metal catalyst, wherein the mass fraction of platinum-cobalt alloy particles in the platinum-based multi-element metal catalyst is about 50 wt%.
Example 8
This example differs from example 1 in that the amount of cobalt chloride added in step (1) was 0.05mmol, and the remaining process parameters and operating procedures were the same as in example 1.
Example 9
This example differs from example 1 in that the amount of cobalt chloride added in step (1) was 1.5mmol, and the remaining process parameters and operating procedures were the same as in example 1.
Example 10
This example differs from example 1 in that the amount of cerium nitrate added in step (1) was 0.005mmol, and the remaining process parameters and the operating procedure were the same as in example 1.
Example 11
This example differs from example 1 in that the amount of cerium nitrate added in step (1) was 0.15mmol, and the remaining process parameters and operating procedure were the same as in example 1.
Example 12
This example is different from example 1 in that the filtrate conductivity in step (2) was 20. mu.S/cm, and the remaining process parameters and operation steps were the same as in example 1.
Comparative example 1
This comparative example provides a commercial catalyst, which is a commercial 50% Pt/C catalyst from Tanaka, Japan.
Comparative example 2
This comparative example differs from example 1 in that cobalt chloride and cerium nitrate in step (1) are omitted and the remaining process parameters and operating steps are the same as in example 1.
Comparative example 3
This comparative example is different from example 1 in that cerium nitrate in step (1) is omitted and the remaining process parameters and operation steps are the same as in example 1.
Comparative example 4
The difference between the comparative example and the example 1 is that the traditional hydrothermal heating mode is adopted in the step (2) to replace the microwave irradiation heating mode, and the rest of process parameters and operation steps are the same as those in the example 1.
The catalysts provided in examples 1 to 12 and comparative examples 1 to 4 were mixed with ionomer and a hydroalcoholic solution to prepare a catalyst slurry, which was then sprayed on both sides of a proton exchange membrane to obtain a fuel cell membrane electrode, and the initial output voltage and the voltage decay after 200 hours were tested, and the results are shown in table 1.
TABLE 1
From the data of table 1, one can see:
(1) the platinum-based multi-element metal catalyst provided in examples 1 to 7 was prepared into a fuel cell membrane electrode, and the open circuit potentials thereof were maintained at 942mV or above, and the attenuations after 200 hours were all at 45mV or below, which was of higher performance and durability, indicating that the platinum-based multi-element metal catalyst obtained by the preparation method of the present invention can improve the oxygen reduction activity of the catalyst, reduce the catalyst production cost, and at the same time, improve the durability of the fuel cell, through the interaction between the platinum transition metal alloy particles and the radical quencher particles.
(2) The open circuit potential of the fuel cell membrane electrode prepared by the platinum-based multi-element metal catalyst provided by the embodiment 8 is lower than that of the fuel cell membrane electrode prepared by the embodiment 1, and the pressure drop after 200 hours is basically the same as that of the fuel cell membrane electrode prepared by the embodiment 1, which shows that the catalyst activity in the embodiment 8 is poor, and the fuel cell has good durability, because the addition amount of the transition metal precursor in the embodiment 8 is too low, the formed platinum transition metal alloy particles are few, the catalyst activity is not favorably improved, and the effect on reducing the platinum dosage is not obvious; the open-circuit potential of the fuel cell membrane electrode prepared by the platinum-based multi-metal catalyst provided by the example 9 is not much different from that of the fuel cell membrane electrode prepared by the example 1, and the pressure drop after 200h is higher than that of the fuel cell membrane electrode prepared by the example 1, which shows that the catalyst in the example 9 has better activity and the fuel cell has poorer durability, because the transition metal precursor in the example 9 is added in an excessive amount, the chemical stability of the catalyst is poor, and the service life of the catalyst is short.
(3) The fuel cell membrane electrode prepared by the platinum-based multi-metal catalyst provided by the embodiment 10 has the open-circuit potential slightly lower than that of the fuel cell membrane electrode prepared by the embodiment 1, and the pressure drop after 200 hours is higher than that of the fuel cell membrane electrode prepared by the embodiment 1; the open-circuit potential of the fuel cell membrane electrode prepared by the platinum-based multi-metal catalyst provided by the embodiment 11 is lower than that of the fuel cell membrane electrode prepared by the embodiment 1, and the pressure drop after 200h is basically the same as that of the fuel cell membrane electrode prepared by the embodiment 1; the reason is that the addition amount of the precursor of the radical quencher in the embodiment 10 is too low, the addition amount of the precursor of the radical quencher in the embodiment 11 is too high, and the addition of the radical quencher can sacrifice the performance of the catalyst to a certain extent to improve the service life of the proton exchange membrane, so that the effect of taking both the performance of the catalyst and the performance of the proton exchange membrane into consideration cannot be achieved due to too low or too high addition amount of the radical quencher.
(4) The open circuit potential of the fuel cell membrane electrode prepared from the platinum-based multi-metal catalyst provided in example 12 is lower than that of example 1, because the conductivity of the filtrate is too high when the catalyst precursor is prepared in example 12, ions in the metal precursor such as chloride ions, nitrate radicals and sulfate radicals are adsorbed on the active sites of the catalyst, and the catalytic activity is shielded.
(5) Comparative example 1 provides a commercial catalyst and a fuel cell membrane electrode prepared with the catalyst having lower catalyst activity and fuel cell stability than example 1; compared with the embodiment 1, the comparative example 2 has no transition metal precursor and no free radical quencher precursor, and has low open-circuit voltage and obvious attenuation after 200 h; comparative example 3 compared with the rest of example 1, the precursor of the free radical quencher is not added, and the attenuation of the open-circuit voltage is obvious after 200 h; compared with the example 1, the open-circuit voltage level of the traditional hydrothermal method is lower by adopting the comparative example 4, which shows that the catalyst prepared by the traditional hydrothermal method has lower activity; therefore, the platinum-based multi-element metal catalyst obtained by the preparation method provided by the invention can improve the oxygen reduction activity of the catalyst, reduce the production cost of the catalyst, improve the durability of the fuel cell and achieve the effect of taking both the performance of the catalyst and the durability of the fuel cell into consideration.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a platinum-based multi-element metal catalyst is characterized by comprising the following steps:
dissolving a platinum precursor, a transition metal precursor, a free radical quencher precursor and a carbon material in a solvent to form reaction slurry, carrying out reduction reaction on the reaction slurry under microwave irradiation to obtain a catalyst precursor, and then carrying out alloying treatment on the catalyst precursor to obtain the platinum-based multi-element metal catalyst.
2. The method according to claim 1, wherein the reaction slurry is prepared by a process comprising:
dissolving the platinum precursor, the transition metal precursor and the free radical quencher precursor in a solvent to form a mixed solution, and then adding the carbon material into the mixed solution for shearing and emulsifying to obtain the reaction slurry;
preferably, alkali is also added into the mixed solution;
preferably, the base comprises sodium hydroxide and/or potassium hydroxide.
3. The preparation method according to claim 1 or 2, characterized in that the molar ratio of the platinum precursor, the transition metal precursor and the radical quencher precursor is 1 (0.1-1) to 0.01-0.1;
preferably, the platinum precursor comprises any one or a combination of at least two of chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate, ammonium chloroplatinate, potassium chloroplatinate, sodium chloroplatinate or platinum acetylacetonate;
preferably, the transition metal precursor comprises any one of nitrate, sulfate, acetylacetonate or chloride of transition metal or a combination of at least two of the two;
preferably, the transition metal in the transition metal precursor includes any one of cobalt, nickel, iron or copper;
preferably, the radical quencher precursor comprises any one of cerium nitrate, manganese nitrate, cerium chloride or manganese chloride;
preferably, the solvent comprises any one of ethanol, ethylene glycol or isopropanol or a combination of at least two thereof;
preferably, the carbon material comprises an activated carbon material;
preferably, the activated carbon material comprises any one of XC-72R, Ketjen black EC-300J, Ketjen black EC-600J, carbon nanotubes, nano graphite powder and graphene or a combination of at least two of the materials;
preferably, the concentration of the carbon material in the solvent is 0.5-10 mg/mL.
4. The preparation method according to claim 2, wherein the rotation speed of the shear emulsification is 8000-13000 rpm/min;
preferably, the time of the shearing emulsification is 0.5-6 h;
preferably, the pH of the reaction slurry is 10-13.
5. The preparation method according to any one of claims 1 to 4, wherein the temperature of the microwave irradiation is 130 to 190 ℃;
preferably, the microwave irradiation time is 2-60 min;
preferably, after the microwave irradiation, filtering, washing and vacuum drying are sequentially carried out to obtain the catalyst precursor;
preferably, the end point of the filtration washing is that the conductivity of the filtrate is less than or equal to 5 mu S/cm.
6. The production method according to any one of claims 1 to 5, wherein the temperature of the alloying treatment is 500 to 1200 ℃;
preferably, the alloying treatment time is 0.5-12 h;
preferably, the alloying treatment is carried out under a protective atmosphere;
preferably, the protective atmosphere comprises nitrogen or argon.
7. The production method according to any one of claims 1 to 6, characterized by comprising:
(1) dissolving a platinum precursor, a transition metal precursor and a free radical quencher precursor into a solvent according to a molar ratio of 1 (0.1-1) to (0.01-0.1), adding alkali to form a mixed solution, then adding a carbon material into the mixed solution, and performing shearing emulsification for 0.5-6 h at a rotating speed of 8000-13000 rpm/min to obtain reaction slurry, wherein the concentration of the carbon material in the solvent is 0.5-10 mg/mL;
(2) carrying out reduction reaction on the reaction slurry obtained in the step (1) for 2-60 min at the microwave irradiation temperature of 130-190 ℃, then filtering and washing until the conductivity of the filtrate is less than or equal to 5 muS/cm, and then carrying out vacuum drying to obtain a catalyst precursor;
(3) and (3) carrying out alloying treatment on the catalyst precursor obtained in the step (2) at the temperature of 500-1200 ℃ for 0.5-12 h under a protective atmosphere to obtain the platinum-based multi-element metal catalyst.
8. A platinum-based multi-metal catalyst, characterized in that it is prepared by the preparation method of any one of claims 1 to 7.
9. The platinum-based multi-metal catalyst according to claim 8, wherein the platinum-based multi-metal catalyst comprises a carbon support, platinum transition metal alloy particles, and radical quencher particles, both of which are supported on the carbon support;
preferably, the mass fraction of the platinum transition metal alloy particles is 10 to 80 wt% based on 100 wt% of the mass fraction of the platinum-based multi-element metal catalyst.
10. Use of a platinum-based multimetallic catalyst as claimed in claim 8 or 9, characterized in that the platinum-based multimetallic catalyst is used in a proton exchange membrane fuel cell.
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