CN114042928B - Preparation method of ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles - Google Patents
Preparation method of ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles Download PDFInfo
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Abstract
The invention discloses a preparation method of ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles, which comprises the following steps: 1. precursor salts of five elements of ruthenium, cobalt, nickel, iron and copper are prepared into solution, and then ammonium chloride is added to be heated and stirred to form mixed homogeneous solution; 2. freeze drying to obtain mixed high-entropy alloy precursor salt; 3. ball-milling to obtain nanometer mixed high-entropy alloy precursor salt; 4. calcining in air, and then carrying out hydrogen reduction to obtain the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles. According to the invention, freeze drying is adopted to ensure the distribution uniformity of each element in the mixed high-entropy alloy precursor salt, so that the phase composition of the product is controlled, nano-crystallization is realized by combining ball milling, and meanwhile, the nano-scale porous structure of the product is realized by adding ammonium chloride into the precursor salt, so that the high-entropy alloy nanoparticles have the advantages of high specific surface area, more active sites and good stability, and have excellent application potential in the fields of catalytic materials, superconducting materials, sensing materials and biological materials.
Description
Technical Field
The invention belongs to the technical field of preparation of nano multi-element alloys, and particularly relates to a preparation method of ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles.
Background
The high-entropy alloy nanoparticles are considered to have huge application potential in the electronic field, the catalysis field, the biological field and the like due to excellent physicochemical properties, and the nanoscale multicomponent alloy is mainly prepared by a liquid phase chemical method due to the limitation of the preparation method at present, so that the nanoscale multicomponent alloy with more than four elements is difficult to prepare, and thus, the preparation of the high-entropy alloy nanoparticles still faces huge challenges.
The high-entropy alloy is firstly proposed by professors in the leaf of scholars in Taiwan area of China, and later people combine the high-entropy alloy with the nano particles to find that the high-entropy alloy has excellent physical and chemical properties, because the high-entropy alloy has the characteristics of the high-entropy alloy (high entropy effect, atomic retardation diffusion effect, serious lattice distortion effect, cocktail effect and high-temperature stability effect) and the characteristics of the nano particles (surface and interface effect, small-size effect, quantum size effect and macroscopic quantum tunneling effect).
The preparation method of the prior multi-element alloy mainly comprises the following steps: the multi-element alloy prepared by a vacuum melting method, a powder metallurgy method, a mechanical alloying method, a laser cladding method and an electrochemical deposition method is mainly in a block shape or a film shape, and the method is not suitable for preparing high-entropy alloy nano particles, so that the preparation of the high-entropy alloy nano particles is always a difficult point of research in the field.
The patent with publication number CN111545767A discloses a preparation method of a nanoscale multicomponent alloy, which prepares a series of high-entropy alloy nanoparticles and comprises the following steps: 1. adding the precursor into ultrapure water to prepare a precursor stable solution; 2. spray drying the precursor stable solution to obtain precursor powder; 3. and calcining the precursor powder to obtain the nanoscale multicomponent alloy. The method comprises the steps of carrying out spray drying and calcination on a precursor steady-state solution to enable all metals in the nanoparticles to be uniformly distributed to form a single-phase solid solution structure or a two-phase structure, and obtaining the nano-scale multi-element alloy or high-entropy alloy nanoparticles which are composed of fourteen metals and have porous structures. Although the method can systematically prepare the high-entropy alloy nanoparticles, the high-entropy alloy nanoparticles have several structures, and the phase of the product is not easy to control.
The application of a multi-element alloy as a tungsten carbide hard alloy binding phase and a preparation method of the tungsten carbide hard alloy are disclosed in a patent with the publication number of CN109295373A, co powder, cr powder, cu powder, fe powder, ni powder and Mo powder are mixed, and then are subjected to ball milling, drying and sieving to prepare CoCrCuFeNiMox multi-element alloy powder; then mixing the prepared high-entropy alloy powder, a ball-milling auxiliary agent and WC powder, and performing ball milling, compression molding and sintering to obtain the high-hardness tungsten carbide hard alloy.
The patent with publication number CN112077331A discloses a preparation method of a carbon-supported nanoscale multicomponent alloy, which systematically describes a preparation process of carbon-supported high-entropy alloy nanoparticles, and comprises the following steps: 1. adding the selected carbon carrier and the prepared precursor salt into deionized water to prepare a stable colloidal solution; 2. atomizing and drying the stable colloid precursor solution to obtain precursor nano particle powder carried by the carbon material; 3. and (3) calcining and reducing the precursor nano particle powder carried by the carbon material to finally obtain the nano-scale multi-element alloy and high-entropy alloy powder carried by the carbon material. The method comprises the steps of mixing a carbon material carrier and precursor salt, carrying out atomization drying, enabling the precursor salt to form nano particles and uniformly load the nano particles on the surface of the carbon material, uniformly distributing all elements in the nano particles, and finally calcining and reducing the precursor nano particle powder loaded on the carbon material to obtain nano-scale multi-element alloy and high-entropy alloy, wherein the multi-element alloy and the high-entropy alloy nano particles are uniformly dispersed on the surface of the carbon material carrier and form a single-phase or multi-phase structure. Although the method is a very effective method for synthesizing carbon-supported high-entropy alloy nanoparticles, the method is a research on the preparation of supported high-entropy alloy nanoparticles, and therefore whether non-supported high-entropy alloy nanoparticles can be prepared is unknown.
Therefore, a preparation method of high-entropy alloy nanoparticles composed of nanoparticles and having a porous structure is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles aiming at the defects of the prior art. The method adopts freeze drying to remove water, prevents element segregation, further controls the phase composition of the product, realizes the nanocrystallization of the nano-mixed high-entropy alloy precursor salt by combining ball milling, and simultaneously realizes the nanoscale porous structure of the product by adding ammonium chloride into the precursor salt and volatilizing and making holes in the calcining process, and the obtained high-entropy alloy nanoparticles have the advantages of high specific surface area, more active sites and good stability.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is characterized by comprising the following steps:
preparing precursor salts of five elements of ruthenium, cobalt, nickel, iron and copper into a solution, adding ammonium chloride, and heating and stirring to form a mixed homogeneous solution;
step two, freeze-drying the mixed homogeneous phase solution formed in the step one to obtain a mixed high-entropy alloy precursor salt;
step three, ball milling the mixed high-entropy alloy precursor salt obtained in the step two to obtain nano mixed high-entropy alloy precursor salt;
and step four, calcining the nano mixed high-entropy alloy precursor salt obtained in the step three in the air, and then carrying out hydrogen reduction to obtain the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles.
According to the invention, precursor salts of metal elements in a target product are prepared into a solution, then ammonium chloride is added to form a mixed homogeneous solution, then the mixed high-entropy alloy precursor salt is obtained through freeze drying and water removal, and the freeze drying treatment ensures that all elements in the mixed high-entropy alloy precursor salt are uniformly distributed, so that element segregation is prevented in the subsequent calcining process, and the phase composition in the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is effectively controlled; and performing ball milling and crushing continuously to obtain nano-mixed high-entropy alloy precursor salt, calcining in the air, volatilizing ammonium chloride in the nano-mixed high-entropy alloy precursor salt in the calcining process, and leaving a large number of nano holes on the surface of the nano-mixed high-entropy alloy precursor salt to form a porous structure, so that the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles obtained by reduction have the advantages of high specific surface area, multiple active sites and good stability, and have excellent application potential in the fields of catalytic materials, superconducting materials, sensing materials and biological materials.
The preparation method of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is characterized in that in the first step, the total metal ion concentration of precursor salt in the mixed homogeneous solution is 0.01mol/L, and the adding mass of ammonium chloride is 2 times of the total mass equivalent of metal elements. The total concentration of the metal ions ensures that all elements in the mixed high-entropy alloy precursor salt are uniformly distributed, the addition quality of the ammonium chloride ensures that a nanoscale hole structure is formed in the calcining process, and the waste of raw materials is avoided.
The preparation method of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles is characterized in that the temperature of freeze drying in the second step is-30 ℃ to-15 ℃, the vacuum degree is 5Pa to 15Pa, and the time is 10h to 20h. According to the invention, by controlling the freeze-drying temperature, the diffusion of each element in the mixed high-entropy alloy precursor salt is effectively prevented, the evaporation of water is accelerated by controlling the vacuum degree, and the complete drying of the mixed high-entropy alloy precursor salt is ensured by combining with the control time.
The preparation method of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is characterized in that the ball milling speed in the third step is 800 r/min-1000 r/min, and the time is 2 h-4 h. The invention leads the mixed high-entropy alloy precursor salt to be completely crushed and nanocrystallized by controlling the rotating speed and time of ball milling.
The preparation method of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is characterized in that the calcining temperature in the fourth step is 300-500 ℃ and the calcining time is 2-4 h, the hydrogen reduction temperature is 500-800 ℃ and the hydrogen reduction time is 1-2 h. According to the invention, the ammonium chloride is completely volatilized by controlling the calcining temperature and time, the nanometer mixed high-entropy alloy precursor salt is completely reduced into the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles by controlling the hydrogen reduction temperature and time, the agglomeration phenomenon and the phase-splitting structure in the high-entropy alloy nanoparticles are prevented, and the quality of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is improved.
One kind ofThe preparation method of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is characterized in that the mass content of each metal element in the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is more than 5 percent in the fourth step, the average particle size of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is 0.1-1 mu m, and the specific surface area is more than 1m 2 The phase structure is a face-centered cubic structure. The phase structure of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is a face-centered cubic structure, so that the structural stability of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is ensured, the performance stability of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is further ensured, meanwhile, the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles have large specific surface area, and the application performance of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is further improved.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, freeze drying is adopted to remove water, so that the distribution uniformity of each element in the mixed high-entropy alloy precursor salt is ensured, element segregation is prevented, the phase composition of the product is further controlled, the nanocrystallization of the nano mixed high-entropy alloy precursor salt is realized by combining ball milling, and meanwhile, the nanoscale porous structure of the product is realized by adding ammonium chloride into the precursor salt, so that the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles have the advantages of high specific surface area, multiple active sites and good stability, and have excellent application potential in the fields of catalytic materials, superconducting materials, sensing materials and biological materials.
2. The mass content of each metal element in the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles prepared by the method is more than 5%, the average particle size of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles is 0.1-1 mu m, and the specific surface area is more than 1m 2 The material has a phase structure of a face-centered cubic structure, and has good structural and performance stability.
3. The preparation method is simple, easy to realize, green and environment-friendly, and is suitable for industrial production.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a flow chart of a preparation process of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles.
FIG. 2 is an SEM image of the Ru-Co-Ni-Fe-Cu high-entropy alloy nanoparticles prepared in example 1 of the invention.
Fig. 3 is an XRD pattern of the ru-co-ni-fe-cu high entropy alloy nanoparticles prepared in example 1 of the present invention.
Detailed Description
Example 1
As shown in fig. 1, the present embodiment includes the following steps:
step one, according to the fact that five metal elements of ruthenium, cobalt, nickel, iron and copper are 1:1:1:1:1, weighing ammonium chlororuthenate, cobalt chloride, nickel chloride, ferric chloride and copper chloride to prepare a solution with the total metal ion concentration of 0.01mol/L, then adding ammonium chloride according to 2 times of the total mass equivalent of metal elements, heating to 80 ℃, stirring and ultrasonically treating for 2 hours to form a mixed homogeneous solution;
step two, placing the mixed homogeneous phase solution formed in the step one in a freeze drying box, and carrying out freeze drying for 15h at the temperature of minus 20 ℃ and the vacuum degree of 10Pa to obtain mixed high-entropy alloy precursor salt;
step three, ball milling the mixed high-entropy alloy precursor salt obtained in the step two for 2 hours at the rotating speed of 800r/min to obtain nano mixed high-entropy alloy precursor salt;
and step four, placing the nano mixed high-entropy alloy precursor salt obtained in the step three into a tube furnace, calcining for 2 hours at 300 ℃ in air, and then carrying out hydrogen reduction for 2 hours at 600 ℃ to obtain the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles.
Through detection, the atomic ratio of each metal element in the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticle prepared in the embodiment is 1:1:1:1:1, the average particle diameter of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles is 0.5 mu m, and the specific surface area is 14.3m 2 The phase structure is a face-centered cubic structure.
Fig. 2 is an SEM image of the ru-co-ni-fe-cu high-entropy alloy nanoparticles prepared in this embodiment, and it can be seen from fig. 2 that the ru-co-ni-fe-cu high-entropy alloy nanoparticles have a particle size of less than 1 μm, are sphere-like powders, and have nanopores on the surface.
Fig. 3 is an XRD pattern of the ru-co-ni-fe-cu high-entropy alloy nanoparticles prepared in this example, and it can be seen from fig. 3 that the ru-co-ni-fe-cu high-entropy alloy nanoparticles have a single-phase face-centered cubic structure.
Example 2
As shown in fig. 1, the present embodiment includes the following steps:
step one, according to the fact that five metal elements of ruthenium, cobalt, nickel, iron and copper are 1:1:1:1:1, weighing ammonium chlororuthenate, cobalt chloride, nickel chloride, ferric chloride and copper chloride to prepare a solution with the total metal ion concentration of 0.01mol/L, then adding ammonium chloride according to 2 times of the total mass equivalent of metal elements, heating to 80 ℃, stirring and ultrasonically treating for 2 hours to form a mixed homogeneous solution;
step two, placing the mixed homogeneous phase solution formed in the step one in a freeze drying box, and carrying out freeze drying for 10 hours at the temperature of minus 15 ℃ and the vacuum degree of 5Pa to obtain mixed high-entropy alloy precursor salt;
step three, ball milling is carried out on the mixed high-entropy alloy precursor salt obtained in the step two for 2 hours under the condition that the rotating speed is 1000r/min, and nano mixed high-entropy alloy precursor salt is obtained;
and step four, placing the nano mixed high-entropy alloy precursor salt obtained in the step three into a tube furnace, calcining for 3 hours at 400 ℃ in the air, and then carrying out hydrogen reduction for 1 hour at 500 ℃ to obtain the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles.
Through detection, the atomic ratio of each metal element in the ru-co-ni-fe-cu high-entropy alloy nanoparticle prepared in this example is 1:1:1:1:1, the average particle diameter of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles is 0.4 mu m, and the specific surface area is 16.7m 2 The phase structure is a face-centered cubic structure.
Example 3
As shown in fig. 1, the present embodiment includes the following steps:
step one, according to the fact that five metal elements of ruthenium, cobalt, nickel, iron and copper are 1:1:1:1:1, weighing ammonium chlororuthenate, cobalt chloride, nickel chloride, ferric chloride and copper chloride to prepare a solution with the total metal ion concentration of 0.01mol/L, then adding ammonium chloride according to 2 times of the total mass equivalent of metal elements, heating to 80 ℃, stirring and ultrasonically treating for 2 hours to form a mixed homogeneous solution;
step two, placing the mixed homogeneous phase solution formed in the step one in a freeze drying box, and carrying out freeze drying for 20 hours at the temperature of minus 30 ℃ and the vacuum degree of 15Pa to obtain mixed high-entropy alloy precursor salt;
step three, ball milling the mixed high-entropy alloy precursor salt obtained in the step two for 4 hours under the condition that the rotating speed is 900r/min to obtain nano mixed high-entropy alloy precursor salt;
and step four, placing the nano mixed high-entropy alloy precursor salt obtained in the step three into a tube furnace, calcining for 2 hours at 500 ℃ in the air, and then carrying out hydrogen reduction for 1 hour at 800 ℃ to obtain the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles.
Through detection, the atomic ratio of each metal element in the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticle prepared in the embodiment is 1:1:1:1:1, the average particle diameter of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles is 0.9 mu m, and the specific surface area is 8.8m 2 The phase structure is a face-centered cubic structure.
Example 4
As shown in fig. 1, the present embodiment includes the following steps:
firstly, according to the condition that five metal elements of ruthenium, cobalt, nickel, iron and copper are 1:1:1:1:1, weighing ammonium chlororuthenate, cobalt chloride, nickel chloride, ferric chloride and copper chloride to prepare a solution with the total metal ion concentration of 0.01mol/L, then adding ammonium chloride according to 2 times of the total mass equivalent of metal elements, heating to 80 ℃, stirring and ultrasonically treating for 2 hours to form a mixed homogeneous solution;
step two, placing the mixed homogeneous phase solution formed in the step one in a freeze drying box, and carrying out freeze drying for 15 hours at the temperature of minus 25 ℃ and the vacuum degree of 13Pa to obtain mixed high-entropy alloy precursor salt;
step three, performing ball milling on the mixed high-entropy alloy precursor salt obtained in the step two for 3 hours under the condition that the rotating speed is 800r/min to obtain nano mixed high-entropy alloy precursor salt;
and step four, placing the nano mixed high-entropy alloy precursor salt obtained in the step three into a tube furnace, calcining for 2 hours at 400 ℃ in the air, and then carrying out hydrogen reduction for 2 hours at 500 ℃ to obtain the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles.
Through detection, the atomic ratio of each metal element in the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticle prepared in the embodiment is 1:1:1:1:1, the average particle diameter of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles is 0.4 mu m, and the specific surface area is 14.7m 2 The phase structure is a face-centered cubic structure.
Example 5
As shown in fig. 1, the present embodiment includes the following steps:
step one, according to the fact that five metal elements of ruthenium, cobalt, nickel, iron and copper are 1:1:1:1:1, weighing ammonium chlororuthenate, cobalt chloride, nickel chloride, ferric chloride and copper chloride to prepare a solution with the total metal ion concentration of 0.01mol/L, then adding ammonium chloride according to 2 times of the total mass equivalent of metal elements, heating to 80 ℃, stirring and ultrasonically treating for 2 hours to form a mixed homogeneous solution;
step two, placing the mixed homogeneous phase solution formed in the step one in a freeze drying box, and carrying out freeze drying for 12 hours at the temperature of minus 20 ℃ and the vacuum degree of 8Pa to obtain mixed high-entropy alloy precursor salt;
step three, ball milling the mixed high-entropy alloy precursor salt obtained in the step two for 3.5 hours under the condition that the rotating speed is 950r/min to obtain nano mixed high-entropy alloy precursor salt;
and step four, placing the nano mixed high-entropy alloy precursor salt obtained in the step three into a tube furnace, calcining for 2 hours at 450 ℃ in the air, and then carrying out hydrogen reduction for 2 hours at 700 ℃ to obtain the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles.
Through detection, the atomic ratio of each metal element in the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticle prepared in the embodiment is 1:1:1:1:1, the average particle diameter of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles is 0.7 mu m, and the specific surface area is 9.3m 2 The phase structure is a face-centered cubic structure.
Example 6
As shown in fig. 1, the present embodiment includes the following steps:
firstly, according to the condition that five metal elements of ruthenium, cobalt, nickel, iron and copper are 1:1:1:1:1, weighing ammonium chlororuthenate, cobalt chloride, nickel chloride, ferric chloride and copper chloride to prepare a solution with the total concentration of metal ions of 0.01mol/L, then adding ammonium chloride according to 2 times of the total mass equivalent of metal elements, heating to 80 ℃, stirring and ultrasonically treating for 2 hours to form a mixed homogeneous solution;
step two, placing the mixed homogeneous phase solution formed in the step one in a freeze drying box, and carrying out freeze drying for 15h at the temperature of minus 28 ℃ and the vacuum degree of 10Pa to obtain mixed high-entropy alloy precursor salt;
step three, ball milling is carried out on the mixed high-entropy alloy precursor salt obtained in the step two for 2 hours under the condition that the rotating speed is 850r/min, and nano mixed high-entropy alloy precursor salt is obtained;
and step four, placing the nano mixed high-entropy alloy precursor salt obtained in the step three into a tube furnace, calcining for 2 hours at 300 ℃ in the air, and then carrying out hydrogen reduction for 2 hours at 500 ℃ to obtain the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles.
Through detection, the atomic ratio of each metal element in the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticle prepared in the embodiment is 1:1:1:1:1, the average particle diameter of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles is 0.5 mu m, and the specific surface area is 15.3m 2 The phase structure is a face-centered cubic structure.
Example 7
As shown in fig. 1, the present embodiment includes the following steps:
step one, according to the fact that five metal elements of ruthenium, cobalt, nickel, iron and copper are 1:1:1:1:1, weighing ammonium chlororuthenate, cobalt chloride, nickel chloride, ferric chloride and copper chloride to prepare a solution with the total metal ion concentration of 0.01mol/L, then adding ammonium chloride according to 2 times of the total mass equivalent of metal elements, heating to 80 ℃, stirring and ultrasonically treating for 2 hours to form a mixed homogeneous solution;
step two, placing the mixed homogeneous phase solution formed in the step one in a freeze drying box, and carrying out freeze drying for 15h at the temperature of minus 28 ℃ and the vacuum degree of 10Pa to obtain mixed high-entropy alloy precursor salt;
step three, ball milling the mixed high-entropy alloy precursor salt obtained in the step two for 2 hours under the condition that the rotating speed is 850r/min to obtain nano mixed high-entropy alloy precursor salt;
and step four, placing the nano mixed high-entropy alloy precursor salt obtained in the step three into a tube furnace, calcining for 4 hours at 300 ℃ in air, and then carrying out hydrogen reduction for 2 hours at 500 ℃ to obtain the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles.
Through detection, the atomic ratio of each metal element in the ru-co-ni-fe-cu high-entropy alloy nanoparticle prepared in this example is 1:1:1:1:1, the average particle diameter of the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles is 0.57 mu m, and the specific surface area is 13.53m 2 The phase structure is a face-centered cubic structure.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (4)
1. A preparation method of ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles is characterized by comprising the following steps:
preparing precursor salts of five elements of ruthenium, cobalt, nickel, iron and copper into a solution, adding ammonium chloride, and heating and stirring to form a mixed homogeneous solution;
step two, freeze-drying the mixed homogeneous phase solution formed in the step one to obtain a mixed high-entropy alloy precursor salt; the temperature of the freeze drying is minus 30 ℃ to minus 15 ℃, the vacuum degree is 5Pa to 15Pa, and the time is 10h to 20h;
step three, ball milling the mixed high-entropy alloy precursor salt obtained in the step two to obtain nano mixed high-entropy alloy precursor salt; the rotation speed of the ball milling is 800 r/min-1000 r/min, and the time is 2h-4h;
and step four, calcining the nano mixed high-entropy alloy precursor salt obtained in the step three in the air, and then carrying out hydrogen reduction to obtain the ruthenium-cobalt-nickel-iron-copper high-entropy alloy nano particles with the nanoscale porous structure.
2. The method for preparing Ru-Co-Ni-Fe-Cu high-entropy alloy nanoparticles as claimed in claim 1, wherein the total metal ion concentration of the precursor salt in the mixed homogeneous solution in the first step is 0.01mol/L, and the added mass of the ammonium chloride is 2 times of the total mass equivalent of the metal elements.
3. The preparation method of the Ru-Co-Ni-Fe-Cu high-entropy alloy nanoparticles as claimed in claim 1, wherein the calcination temperature in the fourth step is 300-500 ℃ for 2h-4 h, and the hydrogen reduction temperature is 500-800 ℃ for 1h-2h.
4. The method for preparing the Ru-Co-Ni-Fe-Cu high-entropy alloy nanoparticles as claimed in claim 1, wherein in the fourth step, the mass content of each metal element in the Ru-Co-Ni-Fe-Cu high-entropy alloy nanoparticles is more than 5%, the average particle size of the Ru-Co-Ni-Fe-Cu high-entropy alloy nanoparticles is 0.1-1 μm, and the specific surface area is more than 1m 2 The phase structure is a face-centered cubic structure.
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