CN112077331A - Preparation method of carbon material-loaded nanoscale multicomponent alloy - Google Patents

Preparation method of carbon material-loaded nanoscale multicomponent alloy Download PDF

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CN112077331A
CN112077331A CN202010946369.7A CN202010946369A CN112077331A CN 112077331 A CN112077331 A CN 112077331A CN 202010946369 A CN202010946369 A CN 202010946369A CN 112077331 A CN112077331 A CN 112077331A
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carbon material
alloy
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loaded
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赵盘巢
操齐高
张卜升
陈昆昆
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Northwest Institute for Non Ferrous Metal Research
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    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
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    • B82—NANOTECHNOLOGY
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    • C01B32/00—Carbon; Compounds thereof
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    • C01B32/198—Graphene oxide
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • D06M2101/40—Fibres of carbon

Abstract

The invention discloses a preparation method of a carbon material-carried nanoscale multicomponent alloy, which comprises the following steps: firstly, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; secondly, atomizing and drying the stable colloidal solution to obtain modified carbon material raw material-carried precursor nano particles; and thirdly, calcining and reducing the precursor-loaded nano particles of the modified carbon material raw material to obtain the powdery carbon material-loaded nanoscale multicomponent alloy. The modified carbon material raw material and the alloy precursor salt are prepared and atomized and dried to enable the alloy precursor salt to form nano particles and to be uniformly loaded on the surface of the carbon material raw material, and then the nano-scale multi-element alloy loaded on the carbon material is obtained by calcining and reducing, and is uniformly dispersed on the surface of the carbon material to form a single-phase structure or a multi-phase structure.

Description

Preparation method of carbon material-loaded nanoscale multicomponent alloy
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method of a carbon material-loaded nanoscale multicomponent alloy.
Background
The multi-element alloy nano particles are widely researched by domestic and foreign researchers as hot materials, and are widely applied to the fields of catalysis, energy storage and the like due to excellent physical and chemical properties. More metal elements are generally mixed together to form the nano alloy material, and the performance of the nano alloy material is expected to exceed that of single alloy or low-element alloy nano particles. The main method for obtaining the multi-element alloy nano particles is a liquid phase chemical method, and the method has obvious advantages in the aspect of preparing the multi-element alloy nano particles with various shapes, particle sizes and phase compositions. However, most of research reports on liquid phase chemical methods show that the alloy composition for preparing the multi-element alloy nanoparticles by the liquid phase chemical method generally does not exceed 4, so that the method limits the synthesis of alloy nanoparticles with more than 5 elements and also hinders the development space of the multi-element alloy nanoparticles. Therefore, the preparation of multi-component alloy nanoparticles with 4 or more than 4 elements still faces the challenge.
The high-entropy alloy is an alloy consisting of more than five metal elements, the ratio of the mole number of each metal element in the alloy to the total mole number of the alloy is between 5% and 35%, the high-entropy alloy generally consists of a single-phase solid solution or a two-phase structure, but does not contain an intermetallic compound phase or other complex phases, and the preparation of the nanoscale multi-element alloy (comprising the high-entropy alloy) consisting of more than four metal elements is still a challenge at present.
The nanoscale multicomponent alloy and the nanoscale high-entropy alloy are nanoscale in particle size, have high specific surface area and a large number of exposed metal active sites, and have a stable phase structure consisting of a single-phase solid solution or a multiphase structure. The nanoscale high-entropy alloy has the characteristics of high-entropy alloy (high-entropy effect, atomic retardation diffusion effect, severe lattice distortion effect, cocktail effect and high-temperature stability effect) and nanoparticles (surface and interface effect, small-size effect, quantum size effect and macroscopic quantum tunneling effect), so that the nanoscale high-entropy alloy has excellent physicochemical properties, and has excellent application potential in the fields of catalytic materials, superconducting materials, chemical sensing materials, biological materials and the like.
In recent years, researchers have prepared multi-element alloys and high-entropy alloy nanoparticles by different methods. An article for preparing multi-component alloy nanoparticles was published by Singh MP et al in Materials Letters in 2015, in which NiFeCrCuCo nanoparticles were synthesized by a wet chemical method. However, due to the limitation of the wet chemical method, more than 5 elements are difficult to be uniformly condensed into a single nano particle, and the method is not suitable for preparing multi-component alloy nano particles with other components. Until 3 months 2018, a Hulian subject group published in the Science journal with a report of synthesizing high-entropy alloy nanoparticles by a carbon thermal impact method, researchers systematically prepare 2-8-element (Pt, Pd, Ni, Co, Fe, Au, Cu and Sn) carbon nanofiber-loaded high-entropy alloy nanoparticles by utilizing a carbon thermal impact method for the first time, explore the catalytic performance of the high-entropy alloy nanoparticles on ammonia oxidation, and the high-entropy alloy nanoparticles show excellent catalytic performance, so that the method breaks through the limitation of a wet chemical method and effectively prepares the 2-8-element high-entropy alloy nanoparticles, but the method has defects, the required experimental conditions are harsh, the cooling rate is required to reach 105K/s, and a reaction matrix (carrier) has good conductivity, so that the subsequent mass preparation and performance control are difficult to meet. An article entitled "preparation of graphene-loaded high-entropy alloy nanoparticles for the first time" is reported by Rekha MY, Nitin M and the like in Scientific Reports in 2018, metal powder and graphene are compounded by using mechanical ball milling, and the compounded metal powder and the graphene are placed in sodium dodecyl sulfate for ultrasound to prepare the graphene-loaded high-entropy alloy nanoparticles (nifecruco), but the method is difficult to promote the uniform distribution of elements in single nanoparticles through ball milling, segregation phenomenon occurs, and the particle size of the prepared nanoparticles is uncontrollable.
The patent with publication number CN108642362A discloses a high-entropy alloy and a preparation method thereof, and the elements in the high-entropy alloy are Cr element, Fe element, Co element, Ni element and Ta element with unequal atomic ratios. Weighing Ta blocks, Co blocks, Cr blocks, Ni blocks and Fe blocks according to the metering ratio of elements of the alloy; and then putting the weighed raw materials into an electric arc melting furnace for melting, and finishing the melting to obtain the high-entropy alloy. The high-entropy alloy prepared by the method is blocky and is not suitable for preparing high-entropy alloy nanoparticles.
Patent publication No. CN105970069A discloses a novel multi-principal-element equi-molar-ratio noble metal high-entropy alloy, which comprises the following elements in terms of mass ratio, in terms of equi-molar-ratio 16.7 ± 0.1 mol% of Au, Pt, Pd, Rh, Ni and Cu: au of 27.2 +/-0.2 wt%, Cu of 8.8 +/-0.2 wt%, Ni of 8.1 +/-0.2 wt%, Pt of 27.0 +/-0.2 wt%, Pd of 14.7 +/-0.2 wt% and Rh of 14.2 +/-0.2 wt%, and a smelting method is adopted to form the high-entropy alloy with a simple solid solution structure. The invention of the alloy combines the high-entropy alloy and the noble metal multi-component alloy, perfects the high-entropy alloy system, develops the design idea and the application field of the noble metal multi-component alloy, and lays a foundation for exploring the theoretical problem and the application value in the noble metal alloy system from a brand-new angle. However, the high-entropy alloy prepared by the method is blocky and is not suitable for preparing high-entropy alloy nanoparticles.
The patent with publication number CN108372294A discloses a high-entropy alloy powder and a preparation method thereof, wherein the high-entropy alloy powder is composed of four elements of Mo, Nb, Ta and W, and the four elements are Mo: nb: ta: w ═ 5-40: (5-40): (5-40): (5-40) preparing high-entropy alloy powder by high-energy ball milling in vacuum after uniformly mixing, taking out the powder, drying in vacuum for 1-5h, and then sieving and grading to obtain the fully alloyed MoNbTaW high-entropy alloy powder with different particle sizes, wherein the diameter of the powder is less than 15 mu m, and the powder can be in the shapes of quasi-spherical shapes, flaky shapes and other irregular shapes. The prepared alloy is micron-level high-entropy alloy and is not suitable for preparing high-entropy alloy nanoparticles.
Therefore, a method for preparing a nano-scale multicomponent alloy loaded with carbon materials, which is composed of nano-particles, is urgently needed.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a carbon material-supported nanoscale multicomponent alloy, aiming at the defects of the prior art. According to the method, a carbon material raw material is modified and then dissolved in deionized water, an alloy precursor salt is added to form a stable colloidal solution, and then atomization drying and calcination reduction are carried out to obtain the carbon material-loaded nanoscale multi-element alloy.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for preparing a carbon material-supported nanoscale multicomponent alloy, which is characterized by comprising a carbon material and a nanoscale multicomponent alloy supported on the carbon material, wherein the nanoscale multicomponent alloy comprises two or more metal elements selected from platinum, cobalt, copper, nickel, iron, ruthenium, tungsten, molybdenum, rhenium, gold, silver, palladium, rhodium and iridium, and the method comprises the following steps:
step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles;
and step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain the powdery carbon material loaded nanoscale multicomponent alloy.
The invention improves the hydrophilicity of the carbon material by modifying the carbon material raw material, forms stable colloid solution by uniformly dispersing the modified carbon material raw material and alloy precursor salt in deionized water, separates out the solution in the stable colloid solution on the surface of the modified carbon material raw material with high hydrophilicity by atomizing and drying the stable colloid solution, ensures that the alloy precursor salt forms nano-scale multi-element alloy and is uniformly loaded on the surface of the modified carbon material raw material, ensures that the particle size of precursor nano-particles formed on the surface of the modified carbon material raw material is smaller, improves the specific surface area of the nano-scale multi-element alloy, realizes uniform dispersion of all metals in the nano-scale multi-element alloy, and fully reduces the precursor nano-particles loaded on the surface of the modified carbon material raw material into the nano-scale multi-element alloy by calcining and reducing the precursor nano-particles loaded on the surface of the modified carbon material raw, preparing the carbon material-carried nanoscale multicomponent alloy with the nanoscale multicomponent alloy uniformly loaded on the surface of the carbon material; the invention leads the grain diameter of the nano-scale multi-element alloy to be smaller by introducing the carbon material, leads the grain diameter of part of the nano-scale multi-element alloy to reach 1nm, improves the specific surface area of the nano-scale multi-element alloy, increases the utilization rate of the nano-scale multi-element alloy in the catalysis process, thereby increasing the conductivity and the catalysis performance of the carbon material loaded nano-scale multi-element alloy, preventing the nano-scale multi-element alloy from agglomerating, reducing the metal consumption and reducing the preparation cost of the nano-scale multi-element alloy.
The preparation method of the carbon material-supported nanoscale multicomponent alloy is characterized in that when the nanoscale multicomponent alloy consists of five or more of platinum, cobalt, copper, nickel, iron, ruthenium, tungsten, molybdenum, rhenium, gold, silver, palladium, rhodium and iridium, the ratio of the mole number of each metal element to the total mole number of the nanoscale multicomponent alloy is 5-35%, and the nanoscale multicomponent alloy is a nanoscale high-entropy alloy. When the nanoscale multicomponent alloy is the nanoscale high-entropy alloy, the carbon material-loaded nanoscale high-entropy alloy has both a high-entropy effect and a nano effect, shows excellent physical and chemical properties, and has excellent application potential in the fields of catalytic materials, superconducting materials, sensing materials, biological materials and the like.
The preparation method of the carbon material-supported nanoscale multicomponent alloy is characterized in that in the step one, the carbon material raw material is graphene oxide, superconducting carbon black, carbon fiber, multi-walled carbon nanotube or nano carbon black.
The preparation method of the carbon material-loaded nanoscale multicomponent alloy is characterized in that the carbon material in the carbon material-loaded nanoscale multicomponent alloy is graphene, superconducting carbon black, carbon fiber, a multi-walled carbon nanotube or nano carbon black. The invention increases the conductivity of the carbon material loaded nanoscale multicomponent alloy, improves the conductivity of the carbon material loaded nanoscale multicomponent alloy in the electrocatalysis process, improves the specific surface area of the carbon material loaded nanoscale multicomponent alloy, improves the utilization rate of the carbon material loaded nanoscale multicomponent alloy, the carbon material-supported nanoscale multicomponent alloy meets the requirement of preparing the carbon material-supported nanoscale multicomponent alloy by using different types of carbon materials, is suitable for different environments, and improves the applicability of the carbon material-supported nanoscale multicomponent alloy.
The preparation method of the carbon material-supported nanoscale multicomponent alloy is characterized in that the particle size of the nanoscale multicomponent alloy is 1 nm-20 nm. The invention controls the grain diameter of the nanoscale multicomponent alloy, so that the grain diameter of the nanoscale multicomponent alloy is smaller, the grain diameter of part of the nanoscale multicomponent alloy can reach 1nm, the specific surface area of the nanoscale multicomponent alloy is improved, the carbon material-loaded nanoscale multicomponent alloy has more metal active sites, the catalytic performance of the carbon material-loaded nanoscale multicomponent alloy is improved, the nanoscale multicomponent alloy is prevented from agglomerating, the shortage of active sites caused by overlarge grain diameter of the nanoscale multicomponent alloy is avoided, and the defects of spontaneous combustion, agglomeration and surface oxidation phenomena caused by high surface energy of the nanoscale multicomponent alloy when the grain diameter of the nanoscale multicomponent alloy is overlarge are avoided.
The preparation method of the carbon material-supported nanoscale multicomponent alloy is characterized in that the nanoscale multicomponent alloy is of a single-phase structure or a multi-phase structure, the single-phase structure is a face-centered cubic structure, a body-centered cubic structure or a close-packed hexagonal structure, and the multi-phase structure is two or three of the face-centered cubic structure, the body-centered cubic structure or the close-packed hexagonal structure. According to the invention, by controlling the structure of the nano-scale multi-element alloy, each metal in the nano-scale multi-element alloy stably exists, the nano-scale multi-element alloy has higher stability, different catalytic reaction types have different requirements on the microstructure of a catalyst, and the carbon material-loaded nano-scale multi-element alloy has various structures, so that the carbon material-loaded nano-scale multi-element alloy can meet various different catalytic reactions, and the applicability of the carbon material-loaded nano-scale multi-element alloy is improved.
The preparation method of the carbon material-supported nanoscale multicomponent alloy is characterized in that the modification process in the step one is as follows: adding a carbon material raw material into a nitric acid solution with the mass fraction of 60-80% to soak for 2-4 h to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 2-5 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 80-90 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is more than two of ammonium chloroplatinate, cobalt chloride, copper nitrate, nickel chloride, ferric nitrate, ruthenium chloride, ammonium tungstate, ammonium molybdate, ammonium rhenate, chloroauric acid, silver nitrate, palladium chloride, rhodium chloride and iridium chloride. The invention adds the carbon material raw material into the nitric acid solution to oxidize the surface of the carbon material raw material, modifies the carbon material raw material, improves the hydrophilicity of the surface of the carbon material raw material, is beneficial to uniformly dispersing nano particles generated by dissolving alloy precursor salt on the surface of the modified carbon material raw material, and enables the particle size of the precursor nano particles separated out from the surface of the modified carbon material raw material in subsequent spray drying to be smaller, thereby reducing the particle size of the nanoscale multicomponent alloy, ensuring the preparation of the subsequent carbon material loaded nanoscale multicomponent alloy, leading the surface of the modified carbon material raw material to have the optimal hydrophilicity by controlling the mass fraction of the nitric acid solution and the modification time, leading the modified carbon material raw material to be uniformly dispersed in deionized water by ultrasonic treatment, forming stable modified carbon material colloidal solution, and having the advantage of improving the production efficiency, the invention is heated, kept warm and stirred, the method has the advantages of completely dissolving alloy precursor salt, better dissolving metal ions, forming stable colloidal solution, accelerating dispersion and improving production efficiency, avoiding the defect that metal ions are hydrolyzed to generate precipitates when the temperature is too high, and avoiding the defect that the dissolving efficiency is too low due to too low temperature.
The preparation method of the carbon material-supported nanoscale multicomponent alloy is characterized in that the atomization drying treatment process in the second step is as follows: keeping the flow of the steady-state colloidal solution at 2.0-4.0 mL/min, the atomization air pressure at 0.5-0.8 MPa, the inlet temperature at 120-220 ℃, and the flow of hot air at 3.0-8.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain the powdery modified carbon material raw material loaded precursor nano particles. The invention uses atomization drying to atomize and disperse the stable colloidal solution containing the modified carbon material raw material at the atomizing nozzle by high-pressure gas to form a large amount of fogdrops containing the modified carbon material raw material, the fogdrops enter a high-temperature drying chamber with hot air, the fogdrops begin to be rapidly dried under the high-temperature condition, solute begins to separate out and crystallize on the surface of the modified carbon material raw material along with the evaporation of solvent to form precursor nano particles, and the stable colloidal solution entering spray drying equipment can be fully spray dried by controlling the flow of the stable colloidal solution because the separation time of the precursor nano particles is extremely short and the components of the precursor nano particles are not fully segregated, so that all elements in the precursor nano particle powder carried by the carbon material are uniformly distributed The rice grains are agglomerated, so that the defect of active sites in the carbon material-loaded nanoscale multicomponent alloy is reduced; according to the invention, by controlling the atomization air pressure, the stable colloidal solution is fully dispersed, and the precursor-loaded nanoparticles of the modified carbon material in the powder state are ensured to have proper particle size, so that the precursor-loaded nanoparticles of the modified carbon material in the powder state are ensured to have more metal active sites, the catalytic performance of the nano-scale multi-element alloy loaded by the carbon material is improved, and the defect that the atomization air pressure exceeds the range to influence the active sites of the nano-scale multi-element alloy loaded by the carbon material is avoided; according to the invention, the inlet temperature is controlled, so that the stable colloidal solution entering the spray drying equipment can be sufficiently spray dried, the defect that agglomeration is generated because spray drying cannot be completely performed due to too low inlet temperature is avoided, and the defect that the oxide or metal simple substance is formed by decomposing part of metal compounds and is not beneficial to later-stage preparation of the carbon material-loaded nanoscale multicomponent alloy due to too high inlet temperature is avoided; according to the invention, the precursor nanoparticles carried by the modified carbon material raw material in a powder state can be smoothly obtained by controlling the flow of hot air, so that the defect that the precursor nanoparticles carried by the modified carbon material raw material in a powder state cannot be efficiently obtained due to too small flow of hot air is avoided, and the defect that the precursor nanoparticles carried by the modified carbon material raw material in a powder state cannot be effectively collected due to too large flow of hot air is avoided; by adopting the process parameters, the particle size of the nanoscale multicomponent alloy in the carbon material-loaded nanoscale multicomponent alloy can be better controlled, and the later-stage calcination process is facilitated.
The preparation method of the carbon material-supported nanoscale multicomponent alloy is characterized in that the calcining reduction process in the third step is as follows: heating the precursor-loaded nano particles of the modified carbon material raw material in a powder state to 300-1000 ℃ at a heating rate of 1-20 ℃/min in a hydrogen atmosphere, then preserving the heat for 1-5h, and then cooling to room temperature at a cooling rate of 1-30 ℃/min. The method is used for calcining in the hydrogen atmosphere, so that the precursor nano particles carried by the powdery modified carbon material are prevented from being oxidized in the calcining process, the precursor nano particle powder is reduced and forms a single-phase structure or a multi-phase structure, and the stable carbon material carried nano-scale multi-element alloy is formed with the modified carbon material; by controlling the heating rate, the invention has the advantages of high production efficiency and uniform heating, avoids the defect of low production efficiency caused by over-low heating rate, and avoids the defect of nonuniform heating of powdery modified carbon material raw material-loaded precursor nano particles caused by over-high heating rate; according to the invention, nanoparticles in the powdery modified carbon material raw material loaded precursor nanoparticles are decomposed and reduced by heating, and then the nanoparticles are completely reduced, so that the nanoscale multicomponent alloy is ensured to be composed of a single-phase structure or a multi-phase structure, and the carbon material loaded nanoscale multicomponent alloy is ensured to have lower oxygen content.
Compared with the prior art, the invention has the following advantages:
1. the invention uniformly disperses the modified carbon material and alloy precursor salt in deionized water to form stable colloidal solution, then carries out atomization drying treatment and calcination reduction, realizes the control of the particle size and element distribution of the nano-scale multi-element alloy, ensures that the nano-scale multi-element alloy carried by the carbon material has the advantages of high specific surface area and multiple metal active sites, ensures that the nano-scale multi-element alloy forms a single-phase structure or a multiphase structure, ensures that the nano-scale multi-element alloy carried by the carbon material has good stability, leads the particle size of the nano-scale multi-element alloy to be smaller by introducing the carbon material, improves the specific surface area of the nano-scale multi-element alloy, increases the utilization rate of the nano-scale multi-element alloy in the catalysis process, increases the conductivity of the nano-scale multi-element alloy carried by the carbon material, and improves the catalytic performance of the nano, prevents the nano-scale multi-component alloy from agglomerating, reduces the using amount of metal and reduces the preparation cost of the nano-scale multi-component alloy.
2. The invention prepares the carbon material-carried nanoscale multi-element alloy with up to fourteen metals combined randomly, can prepare tens of thousands of carbon material-carried nanoscale multi-element alloys with different compositions, increases the applicability of the carbon material-carried nanoscale multi-element alloy, and when the nanoscale multi-element alloy consists of more than five metal elements and forms the nanoscale high-entropy alloy, the prepared carbon material-carried nanoscale high-entropy alloy simultaneously has the characteristics of high-entropy alloy and nano particles, so that the carbon material-carried nanoscale high-entropy alloy has excellent application potential in the fields of catalytic materials, superconducting materials, sensing materials, biological materials and the like.
3. According to the invention, the carbon material raw material is added into the nitric acid solution, so that the surface of the carbon material raw material is oxidized, the carbon material raw material is modified, the hydrophilicity of the surface of the carbon material raw material is increased by modification, precursor nanoparticles generated by dissolving alloy precursor salt are favorably and uniformly dispersed on the surface of the modified carbon material raw material, and the particle size of the precursor nanoparticles separated out from the surface of the modified carbon material raw material in subsequent spray drying is smaller, so that the particle size of the nanoscale multi-element alloy is reduced.
4. According to the invention, through atomization drying, stable colloidal precursor solution is sufficiently atomized and dried, so that all metal elements are uniformly distributed in precursor nano particle powder, the precursor nano particle powder is uniformly loaded on the surface of the modified carbon material raw material, all elements in the powdery modified carbon material raw material loaded precursor nano particles are uniformly distributed, the phenomena of element segregation and particle aggregation in the subsequent preparation process of the nanoscale multi-element alloy are avoided, and meanwhile, the preparation efficiency is improved by using an atomization drying method.
5. According to the invention, the precursor nanoparticles carried by the powdery modified carbon material raw material are calcined and reduced, so that the precursor nanoparticles can be rapidly and completely reduced, the precursor nanoparticles are reduced to form a single-phase structure or a multi-phase structure, a stable carbon material-carried nanoscale multi-component alloy is formed, and the limitation of the traditional method on preparation of the multi-component alloy is broken through.
6. The invention has the advantages of easily obtained raw materials, simple method and low cost, and is suitable for large-scale 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 the preparation of the powdered carbon material supported nanoscale multicomponent alloy of the present invention.
Fig. 2 is a low-power transmission electron microscope image of the powder-state graphene-supported ptcocuioniru nanoscale six-element high-entropy alloy prepared in example 1 of the present invention.
FIG. 3 is a high-power transmission electron microscope image of a powder-state graphene-supported PtCoCuFeNiRu nanoscale six-element high-entropy alloy prepared in example 1 of the present invention.
Fig. 4 is a transmission electron microscope image of low power bright field spherical aberration of the graphene-supported ptcocuiru nanoscale six-membered high-entropy alloy in a powder state prepared in example 1 of the present invention.
Fig. 5 is a high-power bright field spherical aberration transmission electron microscope image of the graphene-supported ptcocuiru nanoscale six-membered high-entropy alloy in a powder state prepared in example 1 of the present invention.
Fig. 6 is a high-power transmission electron microscope dark field image of the powder-state graphene-supported ptcocuioniru nanoscale six-membered high-entropy alloy prepared in example 1 of the present invention.
Fig. 7 is a Cu distribution diagram in a powder-state graphene-supported PtCoCuFeNiRu nanoscale six-membered high-entropy alloy prepared in example 1 of the present invention.
FIG. 8 is a distribution diagram of Fe in the powder-state graphene-supported PtCoCuFeNiRu nanoscale six-membered high-entropy alloy prepared in example 1 of the present invention.
Fig. 9 is a Ni distribution diagram in a powder-state graphene-supported PtCoCuFeNiRu nanoscale six-membered high-entropy alloy prepared in example 1 of the present invention.
Fig. 10 is a distribution diagram of Co in the graphene-supported PtCoCuFeNiRu nanoscale six-membered high-entropy alloy in a powder state prepared in example 1 of the present invention.
FIG. 11 is a Pt distribution diagram in a powder-state graphene-supported PtCoCuFeNiRu nanoscale six-membered high-entropy alloy prepared in example 1 of the present invention.
Fig. 12 is a Ru distribution diagram in the graphene-supported ptcocuifeniru nanoscale six-membered high-entropy alloy in a powder state prepared in example 1 of the present invention.
FIG. 13 is a spherical aberration electron microscope image of a powder-state graphene-supported PtCoCuFeNiRu nanoscale six-membered high-entropy alloy prepared in example 1 of the present invention.
FIG. 14 is an XRD pattern of a graphene-supported PtCoCuFeNiRu nanoscale six-element high-entropy alloy in a powder state prepared in example 1 of the invention.
Detailed Description
As shown in fig. 1, the specific process for preparing the powdered carbon material-supported nanoscale multicomponent alloy of the present invention comprises: the method comprises the steps of modifying a carbon material raw material, preparing an alloy precursor salt to obtain a stable colloidal solution, then carrying out atomization drying on the stable colloidal solution to obtain powdery modified carbon material raw material-carried precursor nanoparticles, and then carrying out calcination reduction on the powdery modified carbon material raw material-carried precursor nanoparticles to obtain powdery carbon material-carried nanoscale multi-element alloy.
Example 1
The carbon material-supported nanoscale multicomponent alloy is a graphene-supported PtCoCuFeNiRu nanoscale six-element high-entropy alloy, wherein the mole numbers of all metal elements are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding a carbon material raw material into a nitric acid solution with the mass fraction of 70% to soak for 3 hours to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 2 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 80 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium chloroplatinate, cobalt chloride, copper nitrate, ferric nitrate, nickel chloride and ruthenium chloride; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material raw material is graphene oxide;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 2.0mL/min, the atomization air pressure at 0.5MPa, the inlet temperature at 160 ℃ and the flow of hot air at 3.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material in a powder state to 500 ℃ at a heating rate of 5 ℃/min in a hydrogen atmosphere, then preserving heat for 3h, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the powder-state graphene-loaded PtCoCuFeNiRu nanoscale six-element high-entropy alloy.
Through detection, in the powder-state graphene-supported PtCoCuFeNiRu nanoscale hexahydric high-entropy alloy prepared in the embodiment, the particle size of the PtCoCuFeNiRu nanoscale hexahydric high-entropy alloy is 1 nm-20 nm, the PtCoCuFeNiRu nanoscale hexahydric high-entropy alloy is uniformly dispersed on the surface of graphene, and all metal elements are uniformly distributed in the PtCoCuFeNiRu nanoscale hexahydric high-entropy alloy to form a face-centered cubic single-phase structure.
Fig. 2 is a low-power transmission electron microscope image of the powdered graphene-supported ptcocucfeniru nanoscale six-membered high-entropy alloy prepared in this embodiment, fig. 3 is a high-power transmission electron microscope image of the powdered graphene-supported ptcocucfeniru nanoscale six-membered high-entropy alloy prepared in this embodiment, fig. 4 is a low-power bright-field image spherical aberration transmission electron microscope image of the powdered graphene-supported ptcocucfeniru nanoscale six-membered high-entropy alloy prepared in this embodiment, fig. 5 is a high-power bright-field image spherical aberration transmission electron microscope image of the powdered graphene-supported ptcocucconiru nanoscale six-membered high-entropy alloy prepared in this embodiment, and as can be seen from fig. 2 to fig. 5, the particle size of the ptcocucfeniru nanoscale high-membered high-entropy alloy in the powdered graphene-supported ptcocucuiru nanoscale high-entropy alloy is 1nm to 20 nm.
Fig. 6 is a dark field image of a high-power transmission electron microscope of a Pt cocucfeniru nanoscale six-membered high-entropy alloy supported by graphene in a powder state prepared in this embodiment, fig. 7 is a Cu distribution diagram in the Pt cocucfeniru nanoscale six-membered high-entropy alloy supported by graphene in a powder state prepared in this embodiment, fig. 8 is a Fe distribution diagram in the Pt cocucfeniru nanoscale six-membered high-entropy alloy supported by graphene in a powder state prepared in this embodiment, fig. 9 is a Ni distribution diagram in the Pt cocucfeniru nanoscale six-membered high-entropy alloy supported by graphene in a powder state prepared in this embodiment, fig. 10 is a Co distribution diagram in the Pt cocucuiru nanoscale high-entropy alloy supported by graphene in a powder state prepared in this embodiment, fig. 11 is a Pt distribution diagram in the Pt cocucuiru nanoscale high-membered high-entropy alloy supported by graphene in a powder state prepared in this embodiment, fig. 12 is a Pt cocucuiru nanoscale high-membered high-entropy alloy supported by graphene in a powder state prepared in this embodiment, and it can be seen from fig. 6 to fig. 11, in the powder-state PtCoCuFeNiRu nanoscale six-element high-entropy alloy prepared by the embodiment, all metal elements are uniformly distributed.
Fig. 13 is a spherical aberration electron microscope image of the powdered graphene-supported ptcocuifernrru nanoscale six-membered high-entropy alloy prepared in this embodiment, and as can be seen from fig. 13, the powdered graphene-supported ptcocuinrru nanoscale six-membered high-entropy alloy prepared in this embodiment forms a face-centered cubic structure, which is a single-phase structure.
Fig. 14 is an XRD pattern of the powdered graphene-supported ptcocucfeniru nanoscale six-membered high-entropy alloy prepared in this embodiment, and as can be seen from fig. 14, a characteristic diffraction peak of the ptcocucfeniru nanoscale six-membered high-entropy alloy and a characteristic diffraction peak of graphene both appear in the powdered graphene-supported ptcocucfeniru nanoscale six-membered high-entropy alloy prepared in this embodiment, and it can be seen that the ptcocucfeniru nanoscale six-membered high-entropy alloy is effectively supported on graphene.
Comparative example 1
This comparative example differs from example 1 in that: in the first step, the carbon material raw material is directly prepared with alloy precursor salt.
Through detection, the particle size of the PtCoCuFeNiRu nanoscale six-membered high-entropy alloy in the powder-state graphene-supported PtCoCuFeNiRu nanoscale six-membered high-entropy alloy prepared by the comparative example is 32 nm-50 nm, and the distribution of the PtCoCuFeNiRu nanoscale six-membered high-entropy alloy on the surface of graphene is uneven.
Comparing the comparative example 1 with the example 1, it can be seen that when the carbon material raw material is not modified, the hydrophilicity of the surface of the carbon material raw material is low, the particle size of the PtCoCuFeNiRu nanoscale six-membered high-entropy alloy formed on the surface of the carbon material raw material is too large, and the PtCoCuFeNiRu nanoscale six-membered high-entropy alloy is not uniformly distributed and does not meet the use requirement.
Comparative example 2
This comparative example differs from example 1 in that the inlet temperature in step two is 110 ℃.
Through detection, the agglomeration phenomenon appears in the powder-state PtCoCuFeNiRu nanoscale six-element high-entropy alloy prepared by the comparative example.
As can be seen by comparing the comparative example 2 with the example 1, in the atomization drying process, when the inlet temperature is lower than 120 ℃, the precursor-loaded nanoparticles of the modified carbon material raw material in the powder state cannot be completely dried in time due to too low atomization temperature, so that the precursor-loaded nanoparticles of the modified carbon material raw material in the powder state are agglomerated under the action of water vapor, and the agglomeration of the PtCoCuFeNiRu nanoscale six-element high-entropy alloy loaded with graphene is caused.
Comparative example 3
This comparative example differs from example 1 in that the inlet temperature in step two is 230 ℃.
Through detection, a phase splitting phenomenon occurs in the PtCoCuFeNiRu nanoscale six-element high-entropy alloy prepared by the comparative example.
Compared with the comparative example 3 and the example 1, it can be seen that in the atomization drying process, when the inlet temperature is higher than 220 ℃, the salt part of the alloy precursor is decomposed and separated out in advance due to too high atomization temperature, so that the phase separation phenomenon occurs in the precursor nano particles carried by the modified carbon material raw material in the powder state, and the phase separation phenomenon occurs in the PtCoCuFeNiRu nanoscale six-element high-entropy alloy carried by graphene.
Comparative example 4
This comparative example differs from example 1 in that the incubation time in step three was 0.5 h.
Through detection, the powder-state graphene-loaded PtCoCuFeNiRu nanoscale six-element high-entropy alloy prepared by the comparative example is not fully reduced.
Compared with the comparative example 4 and the example 1, it can be seen that when the heat preservation time is less than 1h in the calcining process, the precursor nanoparticles carried by the modified carbon material raw material in the powder state can not be sufficiently reduced by reaction due to the excessively short treatment time, so that the prepared powder-state graphene-carried PtCoCuFeNiRu nanoscale six-element high-entropy alloy is not sufficiently reduced.
Comparative example 5
The comparative example differs from example 1 in that the incubation time in step three is 6 hours.
Detection shows that the phase of the generator is separated out from the powder-state graphene-loaded PtCoCuFeNiRu nanoscale six-element high-entropy alloy prepared by the comparative example.
As can be seen by comparing the comparative example 5 with the example 1, when the heat preservation time is more than 5 hours in the calcining process, the phase of the prepared graphene-loaded PtCoCuFeNiRu nanoscale six-element high-entropy alloy in the powder state is separated out due to overlong treatment time.
Example 2
The carbon material-supported nanoscale multi-element alloy is a graphene-supported PtCoCuFe nanoscale four-element alloy, wherein the mole numbers of all metal elements are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding a carbon material raw material into a nitric acid solution with the mass fraction of 80% to soak for 2h to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 5 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 85 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium chloroplatinate, cobalt chloride, copper nitrate and ferric nitrate; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material raw material is graphene oxide;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 3.0mL/min, the atomization air pressure at 0.5MPa, the inlet temperature at 170 ℃ and the flow of hot air at 4.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material in a powder state to 600 ℃ at a heating rate of 8 ℃/min in a hydrogen atmosphere, then preserving heat for 4h, and then cooling to room temperature at a cooling rate of 7 ℃/min to obtain the powder-state graphene-loaded PtCoCuFe nanoscale quaternary alloy.
Through detection, the particle size of the PtCoCuFe nanoscale quaternary alloy in the powder-state graphene-supported PtCoCuFe nanoscale quaternary alloy prepared in the embodiment is 1nm to 20nm, the PtCoCuFe nanoscale quaternary alloy is uniformly dispersed on the surface of graphene, and each metal element is uniformly distributed in the PtCoCuFe nanoscale quaternary alloy, so that a face-centered cubic single-phase structure is formed.
Example 3
The carbon material-supported nanoscale multi-element alloy is a graphene-supported PtCoCuFeNiRuIrRhPdW nanoscale ten-element high-entropy alloy, wherein the mole numbers of all metal elements are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding the carbon material raw material into a nitric acid solution with the mass fraction of 65% to soak for 2.5h to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 3 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 90 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium chloroplatinate, cobalt chloride, copper nitrate, ferric nitrate, nickel chloride, ruthenium chloride, iridium chloride, rhodium chloride, palladium chloride and ammonium tungstate; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material raw material is graphene oxide;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 4.0mL/min, the atomization air pressure at 0.7MPa, the inlet temperature at 190 ℃ and the flow of hot air at 8.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material in a powder state to 400 ℃ at a heating rate of 10 ℃/min in a hydrogen atmosphere, then preserving the heat for 5h, and then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the powder-state graphene-loaded PtCoCuFeNiRuIrRhPdW nanoscale ten-element high-entropy alloy.
Through detection, the particle size of the ptcocucnirurhpdw nanoscale ten-element high-entropy alloy in the powder-state graphene-supported ptcocucuiriirhpdw nanoscale ten-element high-entropy alloy prepared in the embodiment is 1nm to 20nm, the ptcocucucuiriirhpdw nanoscale ten-element high-entropy alloy is uniformly dispersed on the surface of graphene, and each metal element is uniformly distributed in the ptcocucuiriirhpdw nanoscale ten-element high-entropy alloy to form a body-centered cubic single-phase structure.
Example 4
The carbon material-supported nanoscale multicomponent alloy is a graphene-supported PtCoRuCuFeIrNi nanoscale seven-component high-entropy alloy, wherein the mole numbers of all metal elements are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding a carbon material raw material into a nitric acid solution with the mass fraction of 60% to soak for 4 hours to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 4 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 85 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium chloroplatinate, cobalt chloride, ruthenium chloride, copper nitrate, ferric nitrate, iridium chloride and nickel chloride; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material raw material is graphene oxide;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 2.5mL/min, the atomization air pressure at 0.8MPa, the inlet temperature at 210 ℃ and the flow of hot air at 5.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material in a powder state to 800 ℃ at a heating rate of 15 ℃/min in a hydrogen atmosphere, then preserving heat for 2h, and then cooling to room temperature at a cooling rate of 15 ℃/min to obtain the powder-state graphene-loaded PtCoRuCuFeIrNi nanoscale seven-element high-entropy alloy.
Through detection, the particle size of the ptcocucuiferirni nanoscale seven-element high-entropy alloy in the powder-state graphene-supported ptcocucuiferirni nanoscale seven-element high-entropy alloy prepared in the embodiment is 1nm to 20nm, the ptcocucuiferirni nanoscale seven-element high-entropy alloy is uniformly dispersed on the surface of graphene, and each metal element is uniformly distributed in the ptcocucuiferirni nanoscale seven-element high-entropy alloy to form a multiphase structure consisting of face-centered cubic and close-packed hexagonal.
Example 5
The carbon material-loaded nanoscale multicomponent alloy is a graphene-loaded CuFeNiRu nanoscale quaternary alloy, wherein the mole fraction of Fe accounts for 80% of total metals, and the mole numbers of other metal elements are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding the carbon material raw material into a nitric acid solution with the mass fraction of 75% to soak for 3.5h to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 2 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 80 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is copper nitrate, ferric nitrate, nickel chloride and ruthenium chloride; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material raw material is graphene oxide;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 3.5mL/min, the atomization air pressure at 0.6MPa, the inlet temperature at 120 ℃ and the flow of hot air at 7.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material in a powder state to 1000 ℃ at a heating rate of 20 ℃/min in a hydrogen atmosphere, then preserving heat for 1h, and then cooling to room temperature at a cooling rate of 30 ℃/min to obtain the powdery graphene-loaded CuFeNiRu nanoscale quaternary alloy.
Through detection, the particle size of the CuFeNiRu nanoscale quaternary alloy in the powdery graphene-loaded CuFeNiRu nanoscale quaternary alloy prepared in the embodiment is 1-20 nm, the CuFeNiRu nanoscale quaternary alloy is uniformly dispersed on the surface of graphene, and all metal elements are uniformly distributed in the CuFeNiRu nanoscale quaternary alloy to form a close-packed hexagonal single-phase structure.
Example 6
The carbon material-supported nanoscale multicomponent alloy is a carbon black-supported PtCuFeNiRuCoIr nanoscale seven-component high-entropy alloy, wherein the mole fraction of Fe accounts for 35% of total metals, the mole fraction of Ru accounts for 35% of the total metals, and the mole numbers of other metal elements are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding a carbon material raw material into a nitric acid solution with the mass fraction of 80% to soak for 2h to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 4 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 90 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium chloroplatinate, copper nitrate, ferric nitrate, nickel chloride, ruthenium chloride, cobalt chloride and iridium chloride; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material is nano carbon black;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 4.0mL/min, the atomization air pressure at 0.7MPa, the inlet temperature at 220 ℃ and the flow of hot air at 6.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material in a powder state to 700 ℃ at a heating rate of 1 ℃/min in a hydrogen atmosphere, then preserving heat for 4h, and then cooling to room temperature at a cooling rate of 20 ℃/min to obtain the nano carbon black-loaded PtCuFeNiRuCoIr nanoscale seven-element high-entropy alloy in a powder state.
Through detection, the particle size of the ptcufenirucorir nanoscale seven-element high-entropy alloy in the powder-state nano-carbon black-loaded ptcufenirucorir nanoscale seven-element high-entropy alloy prepared in the embodiment is 1nm to 20nm, the ptcufenirucorir nanoscale seven-element high-entropy alloy is uniformly dispersed on the surface of graphene, and all metal elements are uniformly distributed in the ptcufenirucorir nanoscale seven-element high-entropy alloy to form a multi-phase structure consisting of a body-centered cubic structure, a face-centered cubic structure and a close-packed hexagonal structure.
Example 7
The carbon material-supported nanoscale multicomponent alloy is a multiwalled carbon nanotube-supported ReWCoMoRu nanoscale quinary high-entropy alloy, wherein the mole numbers of metal elements are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding the carbon material raw material into a nitric acid solution with the mass fraction of 75% to soak for 2.5h to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 3 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 80 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium rhenate, ammonium tungstate, cobalt chloride, ammonium molybdate and ruthenium chloride; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material is a multi-walled carbon nanotube;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 4.0mL/min, the atomization air pressure at 0.7MPa, the inlet temperature at 200 ℃ and the flow of hot air at 6.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material raw material in a powder state to 300 ℃ at a heating rate of 15 ℃/min in a hydrogen atmosphere, then preserving heat for 5h, and then cooling to room temperature at a cooling rate of 1 ℃/min to obtain the powder-state multiwalled carbon nanotube-loaded ReWCoMoRu nanoscale five-element high-entropy alloy.
Through detection, in the powder-state multiwalled carbon nanotube-supported ReWCoMoRu nanoscale quinary high-entropy alloy prepared in the embodiment, the particle size of the ReWCoMoRu nanoscale quinary high-entropy alloy is 1 nm-20 nm, the ReWCoMoRu nanoscale quinary high-entropy alloy is uniformly dispersed on the surface of graphene, all metal elements are uniformly distributed in the ReWCoMoRu nanoscale quinary high-entropy alloy, and a multiphase structure consisting of a body-centered cube and a face-centered cube is formed.
Example 8
The carbon material-supported nanoscale multicomponent alloy in the embodiment is a carbon fiber-supported PtCuFeNiRuCoIrRh nanoscale eight-component high-entropy alloy, wherein the mole numbers of metal elements are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding a carbon material raw material into a nitric acid solution with the mass fraction of 65% to soak for 3 hours to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 3 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 90 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium chloroplatinate, copper nitrate, ferric nitrate, nickel chloride, ruthenium chloride, cobalt chloride, iridium chloride and rhodium chloride; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material is carbon fiber;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 3.5mL/min, the atomization air pressure at 0.7MPa, the inlet temperature at 140 ℃ and the flow of hot air at 5.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material in a powder state to 900 ℃ at a heating rate of 14 ℃/min in a hydrogen atmosphere, then preserving heat for 1h, and then cooling to room temperature at a cooling rate of 25 ℃/min to obtain the carbon fiber-loaded PtCuFeNiRuCoIrRh nanoscale eight-element high-entropy alloy in a powder state.
Through detection, the particle size of the PtCuFeNiRuCoIrRh nanoscale eight-element high-entropy alloy in the powder-state carbon fiber-supported PtCuFeNiRuCoIrRh nanoscale eight-element high-entropy alloy prepared in the embodiment is 1nm to 20nm, the PtCuFeNiRuCoIrRh nanoscale eight-element high-entropy alloy is uniformly dispersed on the surface of graphene, and all metal elements are uniformly distributed in the PtCuFeNiRuCoIrRh nanoscale eight-element high-entropy alloy to form a face-centered cubic single-phase structure.
Example 9
The carbon material-supported nanoscale multicomponent alloy of the embodiment is a superconducting carbon black-supported PtCoRuCuFeIrNirhPD nanoscale nine-component high-entropy alloy, wherein the mole numbers of metal elements are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding a carbon material raw material into a nitric acid solution with the mass fraction of 70% to soak for 3 hours to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 2 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 90 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium chloroplatinate, cobalt chloride, ruthenium chloride, copper nitrate, ferric nitrate, iridium chloride, nickel chloride, rhodium chloride and palladium chloride; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material is superconducting carbon black;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 3.0mL/min, the atomization air pressure at 0.6MPa, the inlet temperature at 150 ℃ and the flow of hot air at 6.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material in a powder state to 500 ℃ at a heating rate of 4 ℃/min in a hydrogen atmosphere, then preserving heat for 2h, and then cooling to room temperature at a cooling rate of 8 ℃/min to obtain the powder-state superconducting carbon black-loaded PtCoRuFeIrNiRhPD nanoscale nine-element high-entropy alloy.
Through detection, the particle size of the ptcocucuiferirnirhpd nanoscale nine-element high-entropy alloy in the powder-state superconducting carbon black-loaded ptcocucuifernrirrhpd nine-element high-entropy alloy prepared in the embodiment is 1nm to 20nm, the ptcocucuiferirnirhpd nanoscale nine-element high-entropy alloy is uniformly dispersed on the surface of graphene, and each metal element is uniformly distributed in the ptcocucuiferirnirhpd nanoscale nine-element high-entropy alloy to form a face-centered cubic single-phase structure.
Example 10
The carbon material-carried nanoscale multi-element alloy is a superconducting carbon black-carried PtAgAuPdIrhRuCoCuFeNiWMoRe nanoscale ten-element high-entropy alloy, wherein the mole numbers of all metal elements are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding a carbon material raw material into a nitric acid solution with the mass fraction of 80% to soak for 2h to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 5 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 85 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium chloroplatinate, cobalt chloride, copper nitrate, nickel chloride, ferric nitrate, ruthenium chloride, ammonium tungstate, ammonium molybdate, ammonium rhenate, chloroauric acid, silver nitrate, palladium chloride, rhodium chloride and iridium chloride; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material is superconducting carbon black;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 3.5mL/min, the atomization air pressure at 0.5MPa, the inlet temperature at 130 ℃ and the flow of hot air at 7.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material in a powder state to 900 ℃ at a heating rate of 12 ℃/min in a hydrogen atmosphere, then preserving heat for 1h, and then cooling to room temperature at a cooling rate of 18 ℃/min to obtain the PtAgAuPdIrhRuCoCuNiWMoRe nano-scale quaternary high-entropy alloy loaded with the superconducting carbon black in a powder state.
Through detection, in the powdered superconducting carbon black-loaded PtAgAuPdIrrRuCoCuFeNiWMoRe nanoscale quaternary high-entropy alloy prepared in the embodiment, the particle size of the PtAgAuPdIrrRuCoCuFeNiWMoRe nanoscale quaternary high-entropy alloy is 1nm to 20nm, the PtAgAuPdIrrRuCoCuFeNiWMoRe nanoscale quaternary high-entropy alloy is uniformly dispersed on the surface of graphene, and each metal element is uniformly distributed in the PtAgAuPdIrrRuhCoCuFeNiWMoRe nanoscale quaternary high-entropy alloy, so that a multi-phase structure consisting of a body-centered cubic structure and a close-packed hexagonal structure is formed.
Example 11
The carbon material-supported nanoscale multicomponent alloy is a carbon fiber-supported PtCu nanoscale binary alloy, wherein the ratio of the mole number of Pt to the total mole number of the alloy is 99%, and the balance is Cu.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding a carbon material raw material into a nitric acid solution with the mass fraction of 68% to soak for 3h to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 4 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 85 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium chloroplatinate and copper nitrate; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material is carbon fiber;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 4.0mL/min, the atomization air pressure at 0.6MPa, the inlet temperature at 180 ℃ and the flow of hot air at 5.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material in a powder state to 600 ℃ at a heating rate of 7 ℃/min in a hydrogen atmosphere, then preserving the heat for 2h, and then cooling to room temperature at a cooling rate of 23 ℃/min to obtain the carbon fiber-loaded PtCu nanoscale binary alloy in a powder state.
Through detection, the particle size of the PtCu nanoscale binary alloy in the powder carbon fiber-supported PtCu nanoscale binary alloy prepared in the embodiment is 1-20 nm, the PtCu nanoscale binary alloy is uniformly dispersed on the surface of graphene, and all metal elements are uniformly distributed in the PtCu nanoscale binary alloy to form a face-centered cubic single-phase structure.
Example 12
The carbon material-supported nanoscale multicomponent alloy is a multiwalled carbon nanotube-supported PtIrRh nanoscale ternary alloy, wherein the ratio of the mole number of Pt to the total mole number of the alloy is 99.8%, and the ratios of the mole number of the rest metal elements to the total mole number of the alloy are equal.
Step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution; the modification process comprises the following steps: adding a carbon material raw material into a nitric acid solution with the mass fraction of 60% to soak for 4 hours to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 5 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 87 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is ammonium chloroplatinate, rhodium chloride and iridium chloride; the total molar concentration of metal elements in the stable colloidal solution is 0.1 mol/L; the carbon material is a multi-walled carbon nanotube;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles; the atomization drying treatment process comprises the following steps: keeping the flow of the steady-state colloidal solution at 2.5mL/min, the atomization air pressure at 0.8MPa, the inlet temperature at 210 ℃ and the flow of hot air at 7.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain powdery modified carbon material raw material-loaded precursor nanoparticles;
step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain a carbon material loaded nanoscale multicomponent alloy; the calcining reduction process comprises the following steps: heating the precursor-loaded nano particles of the modified carbon material raw material in a powder state to 800 ℃ at a heating rate of 9 ℃/min in a hydrogen atmosphere, then preserving heat for 3h, and then cooling to room temperature at a cooling rate of 30 ℃/min to obtain the powder-state multiwalled carbon nanotube-loaded PtIrRh nanoscale ternary alloy.
Through detection, the particle size of the PtIrRh nanoscale ternary alloy in the powder multi-walled carbon nanotube-supported PtIrRh nanoscale ternary alloy prepared in the embodiment is 1-20 nm, the PtIrRh nanoscale ternary alloy is uniformly dispersed on the surface of graphene, and all metal elements are uniformly distributed in the PtIrRh nanoscale ternary alloy to form a face-centered cubic single-phase 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 (9)

1. A method for preparing a carbon material-supported nanoscale multicomponent alloy, which is characterized by comprising a carbon material and a nanoscale multicomponent alloy supported on the carbon material, wherein the nanoscale multicomponent alloy comprises two or more metal elements selected from platinum, cobalt, copper, nickel, iron, ruthenium, tungsten, molybdenum, rhenium, gold, silver, palladium, rhodium and iridium, and the method comprises the following steps:
step one, modifying a carbon material raw material and preparing the modified carbon material raw material and an alloy precursor salt to obtain a stable colloidal solution;
step two, atomizing and drying the stable colloidal solution obtained in the step one to obtain powdery modified carbon material raw material-carried precursor nanoparticles;
and step three, calcining and reducing the powdery modified carbon material raw material loaded precursor nano particles obtained in the step two to obtain the powdery carbon material loaded nanoscale multicomponent alloy.
2. The method according to claim 1, wherein the nanoscale multicomponent alloy is a nanoscale high-entropy alloy when the nanoscale multicomponent alloy is composed of five or more of platinum, cobalt, copper, nickel, iron, ruthenium, tungsten, molybdenum, rhenium, gold, silver, palladium, rhodium, and iridium, and the ratio of the number of moles of each metal element to the total number of moles of the nanoscale multicomponent alloy is 5% to 35%.
3. The method as claimed in claim 1, wherein the carbon material is graphene oxide, superconducting carbon black, carbon fiber, multi-walled carbon nanotube or nano carbon black.
4. The method according to claim 3, wherein the carbon material in the carbon material-supported nanoscale multicomponent alloy is graphene, superconducting carbon black, carbon fiber, multi-walled carbon nanotube or nano carbon black.
5. The method according to claim 1, wherein the nanoscale multicomponent alloy has a particle size of 1-20 nm.
6. The method for preparing the carbon material supported nanoscale multicomponent alloy as claimed in claim 1, wherein the nanoscale multicomponent alloy has a single-phase structure or a multi-phase structure, the single-phase structure is a face-centered cubic structure, a body-centered cubic structure or a hexagonal close-packed structure, and the multi-phase structure is two or three of the face-centered cubic structure, the body-centered cubic structure or the hexagonal close-packed structure.
7. The method for preparing the carbon material supported nanoscale multicomponent alloy as claimed in claim 1, wherein the modification in step one is as follows: adding a carbon material raw material into a nitric acid solution with the mass fraction of 60-80% to soak for 2-4 h to obtain a modified carbon material raw material; the preparation process comprises the following steps: adding a modified carbon material raw material into deionized water, performing ultrasonic treatment for 2-5 hours to obtain a modified carbon material raw material colloidal solution, heating the modified carbon material raw material colloidal solution to 80-90 ℃, adding an alloy precursor salt, and stirring to obtain a stable colloidal solution; the alloy precursor salt is more than two of ammonium chloroplatinate, cobalt chloride, copper nitrate, nickel chloride, ferric nitrate, ruthenium chloride, ammonium tungstate, ammonium molybdate, ammonium rhenate, chloroauric acid, silver nitrate, palladium chloride, rhodium chloride and iridium chloride.
8. The method for preparing the carbon material supported nanoscale multicomponent alloy as claimed in claim 1, wherein the atomization drying process in step two is as follows: keeping the flow of the steady-state colloidal solution at 2.0-4.0 mL/min, the atomization air pressure at 0.5-0.8 MPa, the inlet temperature at 120-220 ℃, and the flow of hot air at 3.0-8.0L/min, and carrying out atomization drying treatment on the steady-state colloidal solution to obtain the powdery modified carbon material raw material loaded precursor nano particles.
9. The method for preparing the carbon material supported nanoscale multicomponent alloy as claimed in claim 1, wherein the calcination reduction process in step three is as follows: heating the precursor-loaded nano particles of the modified carbon material raw material in a powder state to 300-1000 ℃ at a heating rate of 1-20 ℃/min in a hydrogen atmosphere, then preserving the heat for 1-5h, and then cooling to room temperature at a cooling rate of 1-30 ℃/min.
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