CN115870508A - Preparation method of two-dimensional carbon-based alloy and high-entropy alloy nano material - Google Patents
Preparation method of two-dimensional carbon-based alloy and high-entropy alloy nano material Download PDFInfo
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- CN115870508A CN115870508A CN202211388094.5A CN202211388094A CN115870508A CN 115870508 A CN115870508 A CN 115870508A CN 202211388094 A CN202211388094 A CN 202211388094A CN 115870508 A CN115870508 A CN 115870508A
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Abstract
The invention discloses a preparation method of two-dimensional carbon-based alloy and high-entropy alloy powder, which comprises the following steps: dissolving three or more than three metal salts in triethanolamine according to equal molar ratio, wherein the total molar amount of the metal salts and the molar ratio of the triethanolamine are 1: 4-1: 6, adding a certain amount of ammonium nitrate as an auxiliary agent, stirring for dissolving, heating on a constant-temperature magnetic stirrer until water is completely evaporated, putting into an oven with the set temperature of 300 ℃, and as the temperature rises to 200-250 ℃, emitting a large amount of dense smoke from the solution and burning violently to obtain a fluffy precursor like mushroom cloud. And (3) putting the precursor into a tube furnace, continuously extracting 3 times to exhaust air in vacuum, introducing argon-hydrogen mixed gas (10 percent of hydrogen) and reducing for 2-3 hours at the temperature of 600-800 ℃ to obtain the sheet carbon-based alloy and high-entropy alloy powder. The method has simple process, and the obtained carbon-based high-entropy alloy powder has good conductivity, large specific surface area and uniform dispersion of alloy particles, and is beneficial to industrial production.
Description
Technical Field
The invention relates to an alloy and a high-entropy alloy material and a preparation method thereof, in particular to a preparation method of a two-dimensional carbon-based alloy and a high-entropy alloy nano material.
Background
Metals cover more than 75% of the elements in the periodic table of elements and are widely recognized for their wide application in the fields of optics, electrocatalysis, energy storage and conversion, electronics, medicine, etc. An alloy generally refers to a solid solution consisting of two or more metals or non-metals. Alloying has long been used to impart desirable properties to materials. The design concept of conventional alloys is based on one or two metal elements in excess of 50 atomic percent, with relatively small amounts of secondary elements added to the primary elements, and various processing and treatment processes to produce different alloys. The Taiwan researcher in China proposed the concept of the high-entropy alloy in 1995, but the related concept of the high-entropy alloy is formally proposed in the journal until 2004. The high-entropy alloy has more excellent mechanical properties compared with the traditional alloy due to various complex effects, such as: high strength, high hardness and higher wear resistance and oxidation resistance, and is the key research direction of new metal materials. Extensive research has been conducted on single-phase, dual-phase and multi-phase structures to achieve excellent properties such as high strength, high hardness, good wear resistance, corrosion resistance and high temperature properties. The multi-dimensional composition space that this approach can handle is virtually infinite, and only a small area has been investigated so far. Nevertheless, some high entropy alloys have been demonstrated to have exceptional properties over conventional alloys, and other excellent high entropy alloys are likely to be found in the future. The high mixing entropy in the high-abstraction alloy is beneficial to reducing the free energy of the system, reducing the ordering and segregation tendency of the high-abstraction alloy in the solidification process, particularly at high temperature, and helping the system to form a simple solid solution phase instead of an intermetallic compound with a complex structure. Due to its unique microstructure, good thermal stability, excellent catalytic activity for various reactions, it finds wide application in electro/thermal catalysis, clean energy conversion.
Alloys and high entropy alloys can generally be synthesized by several methods: firstly, smelting and casting can prepare compact solid castings; secondly, a powder metallurgy route can be used for preparing powder metallurgy materials; and thirdly, a deposition technology can be used for preparing films, coatings and the like. Many alloys and high-entropy alloys have harsh preparation conditions and large energy consumption, and the direction of people's efforts on producing the alloys and high-entropy alloy materials on a large scale and reducing the application and production costs is also the direction of people's efforts. In order to enable the alloy and the high-entropy alloy to be widely used in energy conversion, particularly in the catalysis industry, the requirements of good conductivity, large specific surface area, good metal nanoparticle dispersibility and the like which cannot be met by a plurality of processes are also required.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention provides a two-dimensional carbon-based alloy and a high-entropy alloy nano material, and provides a preparation method of the two-dimensional carbon-based alloy and the high-entropy alloy nano material.
The invention is realized by the following technical scheme:
a preparation method of a two-dimensional carbon-based alloy and a high-entropy alloy nano material comprises the following steps:
(1) Three or more transition metal salts are weighed according to the molar equivalent, dissolved in triethanolamine and stirred for dissolution.
(2) Adding auxiliary agent ammonium nitrate into the above solution, heating and stirring at 100 deg.C in a constant temperature magnetic stirrer until water is completely evaporated to obtain brown viscous solution.
(3) The tan viscous solution was placed in an oven set at 300 ℃. And (3) suddenly giving out a large amount of dense smoke from the solution and burning the dense smoke with the temperature rising to 200-250 ℃, instantly rising to 300 ℃, beginning to drop the temperature with the completion of burning, closing the oven at the moment, cooling after the smoke is dispersed, and taking out the precursor fluffy like mushroom cloud.
(4) And putting the precursor into a magnetic boat, putting the magnetic boat into a tube furnace, continuously extracting 3 times of vacuum to exhaust air, and then introducing argon-hydrogen mixed gas (the hydrogen accounts for 10 percent) to reduce for 2 to 3 hours at the temperature of between 500 and 800 ℃, wherein the transition metal oxide generated by the transition metal of the transition metal salt can be reduced by hydrogen to obtain the flaky two-dimensional carbon-based high-entropy alloy powder.
In a preferred embodiment, the transition metal salt includes any one of a transition metal nitrate, a transition metal acetate, and a transition metal chloride.
In a preferred embodiment, the solution is heated for 0.5h at a slow speed because the solution is heated to ensure that the water is evaporated completely and the upper layer of the solution cannot be boiled.
In a preferred embodiment, the temperature rise rate in the precursor reduction process cannot be too fast so as to keep the two-dimensional morphology of the sample and the uniform dispersion of the metal particles, and the temperature is generally selected to be 2-4 ℃/min.
In a preferred embodiment, the transition metal salt comprises Fe (NO) 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O。
In a preferred embodiment, the transition metal salt further comprises Cr (NO) 3 ) 3 ·9H 2 O。
In a preferred embodiment, the transition metal salt further comprises Cu (NO) 3 ) 3 ·3H 2 O。
Compared with the prior art, the invention has the beneficial effects that:
the two-dimensional material takes the carbon layer as a substrate, metal alloy and high-entropy alloy are loaded, the thickness of a lamella is only dozens of nanometers, alloy and high-entropy alloy particles are only 10-20 nanometers, and the material is good in conductivity, large in specific surface and uniform in dispersion.
The method for preparing the carbon-based precursor by one step is simple and convenient, and the two-dimensional carbon-based alloy and the high-entropy alloy nano material can be obtained by subsequent reduction treatment.
Drawings
FIG. 1 is a flow chart of the preparation method of the present application.
FIG. 2 is an XRD spectrum of two-dimensional carbon-based alloy and high-entropy alloy nanomaterials provided in examples 1-3 of the present application;
FIG. 3 is SEM images of two-dimensional carbon-based alloy and high-entropy alloy nanomaterials provided in examples 1-3 of the present application;
FIG. 4 is EDS diagrams of two-dimensional carbon-based alloy and high-entropy alloy nanomaterials provided in examples 1 to 3 of the present application.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
This embodiment 1 provides a method for preparing a two-dimensional carbon-based FeCoNi alloy nanomaterial, where the flow is shown in fig. 1, and the method includes the following steps:
0.01 mol of Fe (NO) 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 And (3) sequentially adding O into beakers filled with 30ml of triethanolamine respectively, stirring uniformly, adding 2g of ammonium nitrate, placing the beakers on a magnetic stirrer with heating for heating and stirring for about 2 hours, and evaporating water to obtain a brown viscous solution. The tan viscous solution was placed in an oven set at 300 ℃. And (3) suddenly giving out a large amount of dense smoke from the solution and burning the dense smoke at the temperature of between 200 and 250 ℃, instantly raising the temperature to 300 ℃, starting to reduce the temperature along with the completion of burning, closing the oven at the moment, and taking out the precursor which is fluffy like mushroom cloud after the smoke is dispersed and cooled. And putting the precursor into a magnetic boat, putting the magnetic boat into a tube furnace, continuously extracting 3 times of vacuum air exhaust, introducing argon-hydrogen mixed gas (the volume of hydrogen accounts for 10 percent) and reducing for 2 to 3 hours at the temperature of between 500 and 800 ℃ to obtain the flaky two-dimensional carbon-based high-entropy alloy powder.
Example 2
The embodiment 2 provides a preparation method of a two-dimensional carbon-based FeCoNiCr alloy nano material, the flow is shown in FIG. 1, and the preparation method comprises the following steps:
0.01 mol of Fe (NO) 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Cr(NO 3 ) 3 ·9H 2 And (3) sequentially adding O into beakers filled with 40ml of triethanolamine, stirring uniformly, adding 3g of ammonium nitrate, placing the beakers on a magnetic stirrer with heating for heating and stirring for about 2 hours, and evaporating water to obtain brown viscous solution. The tan viscous solution was placed in an oven set at 300 ℃. And (3) suddenly giving out a large amount of dense smoke from the solution and burning the dense smoke at the temperature of between 200 and 250 ℃, instantly raising the temperature to 300 ℃, starting to reduce the temperature along with the completion of burning, closing the oven at the moment, and taking out the precursor which is fluffy like mushroom cloud after the smoke is dispersed and cooled. And putting the precursor into a magnetic boat, putting the magnetic boat into a tube furnace, continuously extracting 3 times of vacuum air exhaust, introducing argon-hydrogen mixed gas (the volume of hydrogen accounts for 10 percent) and reducing for 2 to 3 hours at the temperature of between 500 and 800 ℃ to obtain the flaky two-dimensional carbon-based high-entropy alloy powder.
Example 3
The embodiment 2 provides a preparation method of a two-dimensional carbon-based FeCoNiCrCu alloy nano material, the flow of which is shown in FIG. 1, and the method comprises the following steps:
0.01 mol of Fe (NO) 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Cr(NO 3 ) 3 ·9H 2 O、 Cu(NO 3 ) 3 ·3H 2 And O. Respectively and sequentially adding the mixture into beakers filled with 45ml of triethanolamine, uniformly stirring, adding 4g of ammonium nitrate, placing the beakers on a magnetic stirrer with heating for heating and stirring for about 2 hours, and evaporating water to obtain brown viscous solution. The tan viscous solution was placed in an oven set at 300 ℃. And (3) suddenly giving out a large amount of dense smoke from the solution and burning the dense smoke at the temperature of between 200 and 250 ℃, instantly raising the temperature to 300 ℃, starting to reduce the temperature along with the completion of burning, closing the oven at the moment, and taking out the precursor which is fluffy like mushroom cloud after the smoke is dispersed and cooled. And putting the precursor into a magnetic boat, putting the magnetic boat into a tube furnace, continuously extracting 3 times of vacuum air exhaust, introducing argon-hydrogen mixed gas (the volume of hydrogen accounts for 10 percent) and reducing for 2 to 3 hours at the temperature of between 500 and 800 ℃ to obtain the flaky two-dimensional carbon-based high-entropy alloy powder.
Fig. 2 shows XRD patterns of the two-dimensional carbon-based alloy and the high-entropy alloy nano-material provided in examples 1 to 3, and it can be seen from the XRD patterns that the two-dimensional carbon-based FeCoNi alloy, the two-dimensional carbon-based FeCoNiCr alloy, and the two-dimensional carbon-based FeCoNiCrCu high-entropy alloy all show a face-centered cubic (FCC) structure. FIG. 3 is SEM images of two-dimensional carbon-based alloy and high-entropy alloy nanomaterials provided in examples 1 to 3, wherein the materials are shown to exhibit two-dimensional nano-flakes; fig. 4 is an EDS diagram of two-dimensional carbon-based alloy and high-entropy alloy nanomaterials provided in examples 1 to 3, and it can be seen from the diagram that each metal element is uniformly dispersed on the two-dimensional carbon-based nanosheet.
The foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that various changes, modifications and substitutions may be made by those skilled in the art without departing from the spirit of the invention, and all are intended to be included within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (9)
1. A preparation method of a two-dimensional carbon-based alloy and a high-entropy alloy nano material is characterized by comprising the following steps:
s1, weighing three or more transition metal salts according to equimolar proportion, dissolving the transition metal salts into triethanolamine, and stirring the transition metal salts to dissolve the transition metal salts into a solution;
s2, adding an auxiliary agent ammonium nitrate into the solution, heating and stirring the solution on a constant-temperature magnetic stirrer at 100 ℃ until water is completely evaporated to obtain a brown viscous solution;
s3, placing the brown viscous solution into an oven with the set temperature of 300 ℃, suddenly emitting a large amount of dense smoke and burning the dense smoke along with the temperature rise to 200-250 ℃, instantly raising the temperature to 300 ℃, beginning to reduce the temperature along with the end of burning, closing the oven at the moment, and taking out a fluffy precursor after the smoke is dispersed and cooled;
and S4, putting the precursor into a magnetic boat, putting the magnetic boat into a tubular furnace, continuously extracting 3 times of vacuum to exhaust air, introducing argon-hydrogen mixed gas, and reducing for 2-3 hours at the temperature of 500-800 ℃, wherein transition metal oxides generated by transition metals of the transition metal salts can be reduced by hydrogen to obtain the flaky two-dimensional carbon-based alloy and the high-entropy alloy powder.
2. A method according to claim 1, wherein the transition metal salt comprises a transition metal nitrate.
3. The preparation method of the two-dimensional carbon-based alloy and high-entropy alloy nano-material according to claim 1, wherein the heating time in the step S2 is 0.5h.
4. The preparation method of the two-dimensional carbon-based alloy and the high-entropy alloy nanomaterial according to claim 1, wherein a temperature rise rate in a reduction process of the precursor in the step S4 is 2-4 ℃/min.
5. The preparation method of the two-dimensional carbon-based alloy and high-entropy alloy nano-material according to claim 1, wherein a hydrogen volume of the argon-hydrogen mixed gas in the step S4 accounts for 10% of the volume of the two-dimensional carbon-based alloy and high-entropy alloy nano-material.
6. A method according to claim 2, wherein the transition metal nitrate comprises Fe (NO) 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O。
7. A method according to claim 6, wherein the transition metal nitrate further comprises Cr (NO) 3 ) 3 ·9H 2 O。
8. A two-layer film according to claim 6The preparation method of the wiener-based alloy and the high-entropy alloy nano material is characterized in that the transition metal nitrate also comprises Cu (NO) 3 ) 3 ·3H 2 O。
9. Two-dimensional carbon-based alloy and high-entropy alloy nano-material prepared by the method of any one of claims 1 to 8.
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