CN112551528A - Preparation method of polyhedral transition metal carbide particles for catalytic material - Google Patents

Preparation method of polyhedral transition metal carbide particles for catalytic material Download PDF

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CN112551528A
CN112551528A CN202011394706.2A CN202011394706A CN112551528A CN 112551528 A CN112551528 A CN 112551528A CN 202011394706 A CN202011394706 A CN 202011394706A CN 112551528 A CN112551528 A CN 112551528A
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transition metal
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metal carbide
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CN112551528B (en
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赵庆龙
金伟
姜启川
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Jilin University
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Abstract

The invention discloses a preparation method of polyhedral transition metal carbide particles for catalytic materials, which comprises the following steps: step 1, uniformly mixing aluminum powder, transition metal powder and a carbon source by ball milling, and pressing into a preparation block; wherein the transition metal powder comprises titanium powder, tantalum powder, niobium powder, zirconium powder, tungsten powder and/or vanadium powder; the content of the aluminum powder is 40-70 wt.%, and the molar ratio of the carbon source to the transition metal powder is 0.5-0.8; step 2, heating the preparation block in a vacuum or argon protection state and then cooling to room temperature; and 3, soaking with hydrochloric acid to remove the aluminum matrix to obtain polyhedral transition metal carbide particles. The method provided by the invention prepares nano polyhedral transition metal carbide particles by combining medium-low temperature and high temperature and rapidly cooling respectively, and prepares submicron and micron polyhedral transition metal carbide particles by secondary heating.

Description

Preparation method of polyhedral transition metal carbide particles for catalytic material
Technical Field
The invention relates to the technical field of ultrahigh-temperature ceramic materials, in particular to a preparation method of polyhedral transition metal carbide particles for catalytic materials.
Background
Transition metal carbides have the advantages of high melting point, high hardness, good electrical conductivity and chemical stability, and are widely used as coating materials, mechanical parts and reinforcing phases in composite materials. Transition metal carbides have attracted considerable attention in catalytic applications since the first reports by Levy and Boudart in 1973 that WC has catalytic properties similar to metals of the Pt group in the isomerization of neopentane. When the transition metal carbide particles are used as a reinforcing phase of a composite material, the morphology of the particles is generally desired to be nearly spherical or spherical, and when the shape of the particles is regular polyhedron, adverse effects such as substrate fracture and material plasticity reduction can be caused, so that most methods for preparing the transition metal carbide particles are dedicated to preparing the nearly spherical or spherical particles; however, when the transition metal carbide is used as a catalytic material, it is necessary that the particles are regular polyhedrons, since the catalytic effect is affected by a specific crystal plane, and there is little report on a method for preparing the regular polyhedral transition metal carbide. Compared with Pt group metals, the transition metal carbide has rich sources, low cost and strong tolerance to the poisoning action of the catalyst, and is a catalytic material with wide application prospect.
In the prior art, the preparation method of the transition metal carbide is a self-propagating high-temperature preparation technology, but in the process of preparing the transition metal carbide, the preparation process cannot be controlled due to the fact that the combustion reaction speed is high, a large amount of heat is released, and the temperature field is not uniform, so that the prepared particles are not uniform in size, and even the morphology may be irregular.
At present, the problem that the transition metal carbide cannot be prepared controllably on a large scale and the size, morphology and specific crystal face of the transition metal carbide cannot be well controlled limits the practical application of the transition metal carbide in catalysis, and therefore, the development of a carbide particle with regular morphology, uniform size and high catalytic activity is urgently needed.
Disclosure of Invention
The invention aims to design and develop a preparation method of polyhedral transition metal carbide particles for catalytic materials, and polyhedral transition metal carbide with regular particle appearance and uniform size is prepared by regulating the content of aluminum powder and transition metal powder and the proportion of the transition metal powder and a carbon source, so that the catalytic effect is greatly improved; and the transition metal powder is formed by solid solution of single element or multiple elements, so that the prepared multi-element transition metal carbide particles have different properties.
The invention also aims to design and develop a preparation method of polyhedral transition metal carbide particles for catalytic materials, which is used for preparing nano polyhedral transition metal carbide particles with polyhedral particle morphology, uniform and fine particle size and larger specific surface area by a medium-low temperature heating method.
The invention also aims to design and develop a preparation method of polyhedral transition metal carbide particles for catalytic materials, which is used for preparing nano transition metal carbide particles with more regular particle morphology and high defect concentration in carbide crystals by combining a high-temperature heating method with rapid cooling.
The invention also aims to design and develop a preparation method of polyhedral transition metal carbide particles for catalytic materials, which is used for preparing submicron and micron polyhedral transition metal carbide particles with uniform particle size and regular appearance by a heating method of secondary heating.
The technical scheme provided by the invention is as follows:
a preparation method of polyhedral transition metal carbide particles for catalytic materials comprises the following steps:
step 1, uniformly mixing aluminum powder, transition metal powder and a carbon source by ball milling, and pressing into a preparation block;
wherein the transition metal powder comprises titanium powder, tantalum powder, niobium powder, zirconium powder, tungsten powder and/or vanadium powder;
the content of the aluminum powder is 40-70 wt.%, and the molar ratio of the carbon source to the transition metal powder is 0.5-0.8;
step 2, heating the preparation block under the vacuum or argon protection state, cooling to room temperature and taking out;
and 3, soaking with hydrochloric acid to remove the aluminum matrix to obtain polyhedral transition metal carbide particles.
Preferably, in the step 2, the preparation block is heated to 700 ℃ under vacuum or argon protection, and is cooled to room temperature after heat preservation for 30-90 minutes, and then taken out.
Preferably, in the step 2, before the preliminary block is heated in a vacuum or argon protection state, the tubular heating furnace is heated to 1000-1600 ℃ for heat preservation, the preliminary block is covered with molybdenum wires and hung into the furnace for heat preservation, and after the preliminary block is ignited, the preliminary block is rapidly cooled by using high-temperature quenching oil or water.
Preferably, in the step 2, the preparation block is heated to 800 ℃ under vacuum or argon protection, the temperature is maintained for 30min, then the preparation block is continuously heated to 1600 ℃ under 1000 ℃ and the temperature is maintained for 1min to 100min, and the preparation block is taken out for air cooling or furnace cooling after the temperature is maintained.
Preferably, in the step 1, a ball mill is adopted for mixing, the ball mass ratio of the ball mill is 5:1-20:1, the rotating speed of the ball mill is 50-100r/min, and the ball milling time is 8-24 h.
Preferably, in the step 1, the purity of the aluminum powder is greater than 99.9%, and the purity of the transition metal powder is greater than 99.9%.
Preferably, in the step 1, the preliminary block has a cylindrical shape, and the preliminary block is placed in a graphite grinding tool after being formed.
Preferably, in the step 1, the carbon source is carbon black or CNTs.
Preferably, in the step 2, the heating is performed by a heating furnace, and the heating furnace is a vacuum hot-pressing sintering furnace, a tube furnace or an electromagnetic induction melting furnace.
Preferably, the heating rate of the heating furnace is 5-30 ℃/min; if the heating is carried out under vacuum, the degree of vacuum should be 10 Pa.
The invention has the following beneficial effects:
(1) the nanometer transition metal carbide particles are prepared at medium and low temperature, the temperature does not reach the ignition temperature of combustion reaction, and the prepared particles have uniform and fine size (less than or equal to 50nm), polyhedral appearance and larger specific surface area due to very low temperature, relatively uniform temperature field and relatively slow particle growth rate.
(2) The nano transition metal carbide particles are prepared by combining high temperature with rapid cooling, and the pressed blocks are rapidly cooled at the moment of just igniting, so that the states of uniform and fine (50-100nm) size and regular appearance at the initial growth stage of the crystal are kept, the phenomena of non-uniform size and irregular appearance caused by the continuous growth of the crystal in a non-uniform temperature field generated in the self-propagating combustion process are avoided, the reaction is sufficient, the preparation process is short, the concentration of defects in the carbide crystal is high, and the catalytic activity is higher.
(3) When the prefabricated block is heated to 800 ℃ along with the furnace and is kept warm for 30min, a large amount of nano transition metal carbide particles are formed, when the temperature is continuously raised to 1600 ℃ along with the furnace, the heat released by combustion reaction is little, and the whole prefabricated block is in a uniform temperature field, so that the prepared polyhedral carbide particles are uniform in size and regular in shape, and meanwhile, the transition metal carbide particles with different sizes can be obtained by keeping warm at different temperatures for different times.
(4) The morphology and specific crystal faces of the prepared transition metal carbide are well controlled by regulating the Al content and the M/C ratio, so that carbide particles which are multi-scale, regular in morphology, uniform in size, have specific crystal faces and high in catalytic activity are prepared.
Drawings
FIG. 1 is a field emission diagram of a transition metal carbide prepared in example 2 of the present invention.
Fig. 2 is an XRD spectrum of the transition metal carbide prepared in example 11 according to the present invention.
FIG. 3 is a field emission diagram of a transition metal carbide prepared in example 11 according to the present invention.
Fig. 4 is an SEM picture of transition metal carbide prepared in example 20 according to the present invention.
Fig. 5 is an SEM image of transition metal carbide prepared in example 28 according to the present invention.
Fig. 6 is an SEM picture of transition metal carbide prepared in example 29 according to the present invention.
Fig. 7 is a field emission diagram of the transition metal carbide prepared in comparative example 1 according to the present invention.
FIG. 8 is a field emission diagram of a transition metal carbide prepared in comparative example 4 according to the present invention.
Detailed Description
The present invention is described in further detail below in order to enable those skilled in the art to practice the invention with reference to the description.
The invention provides a preparation method of polyhedral transition metal carbide particles for catalytic materials, which comprises the following steps:
step 1, uniformly mixing aluminum powder, transition metal powder and a carbon source in a ball mill, wherein the ball-material mass ratio of the ball mill is 5:1-20:1, the rotating speed of the ball mill is 50-100r/min, and the ball milling time is 8-24 h; taking out the uniformly mixed powder, wrapping the uniformly mixed powder with an aluminum foil, pressing the uniformly mixed powder into a cylindrical preparation block, and then placing the cylindrical preparation block into a graphite grinding tool;
wherein the transition metal powder comprises titanium powder, tantalum powder, niobium powder, zirconium powder, tungsten powder and/or vanadium powder; the carbon source is carbon black or CNTs.
The content of the aluminum powder is 40-70 wt.%, and the molar ratio of the carbon source to the transition metal powder is 0.5-0.8; the purity of the aluminum powder is more than 99.9%, and the purity of the transition metal powder is more than 99.9%.
Step 2, heating the preparation block under the vacuum or argon protection state, cooling to room temperature in different modes, and taking out;
wherein, when preparing nanometer transition metal carbide particles at medium and low temperature, the preparation block is heated to 700-;
when nano transition metal carbide particles are prepared under high-temperature combined rapid cooling, before the preparation block is heated in a vacuum or argon protection state, the tubular heating furnace is heated to 1000-1600 ℃ for heat preservation, the preparation block is coated by molybdenum wires and hung into the furnace for heat preservation, and after the preparation block is ignited, rapid cooling is immediately carried out by using high-temperature quenching oil or water.
When submicron and micron polyhedral transition metal carbide particles are prepared by secondary heating, the preparation block is heated to 800 ℃ in vacuum or in an argon protection state, the temperature is preserved for 30min, then the preparation block is continuously heated to 1600 ℃ in 1000 ℃ and the temperature is preserved for 1min-100min, and the preparation block is taken out for air cooling or furnace cooling after the temperature preservation is finished.
Heating is carried out through a heating furnace, and the heating rate of the heating furnace is 5-30 ℃/min, wherein the heating furnace is a vacuum hot-pressing sintering furnace, a tube furnace or an electromagnetic induction smelting furnace; if the heating is carried out in a vacuum state, the vacuum degree should reach 10 Pa.
And 3, extracting the prepared block by using hydrochloric acid, and corroding the aluminum matrix to obtain transition metal carbide particles serving as catalytic materials.
Example 1:
preparing nanometer polyhedral TiC particles with uniform size and regular shape at low temperature: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 40 wt%, the molar ratio of C to Ti is 0.6, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the TiC particles prepared are extracted from the aluminum matrix by concentrated hydrochloric acid, and the TiC particles are about 50nm fine in size and nearly octahedral in shape.
Example 2:
preparing nanometer polyhedral TiC particles with uniform size and regular shape at low temperature: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 60 wt%, the molar ratio of C to Ti is 0.6, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the TiC particles prepared were extracted from the aluminum matrix using concentrated hydrochloric acid, the size and morphology of which are shown in fig. 1.
Example 3:
preparing nanometer polyhedral TiC particles with uniform size and regular shape at low temperature: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 70 wt%, the molar ratio of C to Ti is 0.6, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the TiC particles prepared were extracted from the aluminum matrix using concentrated hydrochloric acid, which was about 40nm fine in size and nearly octahedral in morphology.
Example 4:
preparing nanometer polyhedral TiC particles with uniform size and regular shape at low temperature: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 40 wt%, the molar ratio of C to Ti is 0.5, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the prepared TiC particles are extracted from the aluminum matrix by concentrated hydrochloric acid, and the size and the shape of the TiC particles are approximate octahedron of about 50 nm.
Example 5:
preparing nanometer polyhedral TiC particles with uniform size and regular shape at low temperature: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 60 wt%, the molar ratio of C to Ti is 0.5, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the prepared TiC particles are extracted from the aluminum matrix by concentrated hydrochloric acid, and the size and the shape of the TiC particles are approximate octahedron of about 50 nm.
Example 6:
preparing nanometer polyhedral TiC particles with uniform size and regular shape at low temperature: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 70 wt%, the molar ratio of C to Ti is 0.5, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the prepared TiC particles are extracted from the aluminum matrix by concentrated hydrochloric acid, and the size and the appearance of the TiC particles are nearly octahedron of about 40 nm.
Example 7:
preparing nanometer polyhedral TiC particles with uniform size and regular shape at low temperature: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 40 wt%, the molar ratio of C to Ti is 0.8, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the prepared TiC particles are extracted from the aluminum matrix by concentrated hydrochloric acid, and the size and the shape of the TiC particles are approximate octahedron of about 50 nm.
Example 8:
preparing nanometer polyhedral TiC particles with uniform size and regular shape at low temperature: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 60 wt%, the molar ratio of C to Ti is 0.8, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the prepared TiC particles are extracted from the aluminum matrix by concentrated hydrochloric acid, and the size and the shape of the TiC particles are approximate octahedron of about 50 nm.
Example 9:
preparing nanometer polyhedral TiC particles with uniform size and regular shape at low temperature: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 70 wt%, the molar ratio of C to Ti is 0.8, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the prepared TiC particles are extracted from the aluminum matrix by concentrated hydrochloric acid, and the size and the appearance of the TiC particles are nearly octahedron of about 40 nm.
Comparative example 1:
when the C/M molar ratio is higher, polyhedral carbides with regular shapes can not be prepared, and the carbides can be transformed to be spherical. Firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 70 wt%, the molar ratio of C to Ti is 0.4, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the TiC particles prepared are extracted from the aluminum matrix using concentrated hydrochloric acid, which, although small in size, tend to be nearly spherical in morphology.
Comparative example 2:
when the C/M molar ratio is lower, the polyhedral carbide with regular shape and appearance can not be prepared, and the carbide can be transformed to be spherical. Firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 70 wt%, the molar ratio of C to Ti is 1.0, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And then, putting the pressed cylindrical block into a self-made graphite mold, putting the cylindrical block and the self-made graphite mold into a vacuum hot-pressing sintering furnace, starting heating after vacuumizing is finished, wherein the vacuum degree is kept below 10Pa, the heating rate is 30 ℃/min, preserving heat for 30min when the temperature of the vacuum hot-pressing sintering furnace is raised to 700 ℃, stopping heating, and taking out a product after the product is cooled to the room temperature.
Finally, the TiC particles prepared are extracted from the aluminum matrix using concentrated hydrochloric acid, which, although small in size, tend to be nearly spherical in morphology.
Further description with respect to the above examples and comparative examples: regarding the temperature range, if the temperature is lower than 660 ℃, wherein Al powder, Ti powder and CNTs are all solid phases, the reaction rate is extremely slow; if the temperature is higher than 880 ℃, the combustion synthesis reaction conditions of the system can be triggered, and the reaction process can not be controlled, so that the temperature is selected to be about 700-800 ℃ to meet the test requirements, and the temperature and the time can be properly adjusted according to the components.
The invention relates to a preparation method of polyhedral transition metal carbide particles for catalytic materials, which is designed and developed by the invention, through regulating and controlling the contents of aluminum powder and transition metal powder, nanometer transition metal carbide particles are prepared at medium and low temperature, the temperature does not reach the ignition temperature of combustion reaction, and because the temperature is very low and the temperature field is relatively uniform, the particle growth rate is relatively slow, the prepared particles are uniform and fine (less than or equal to 50nm), are polyhedral in appearance and have relatively large specific surface area; and the transition metal powder is formed by solid solution of single element or multiple elements, so that the prepared multi-element transition metal carbide particles have different properties.
Example 10:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 40 wt%, and the molar ratio of C to Ti is 0.6. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, and the TiC particles are regular and nearly octahedral and have uniform sizes.
Example 11:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 50 wt%, and the molar ratio of C to Ti is 0.6. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the TiC particles prepared were extracted from the aluminum matrix using concentrated hydrochloric acid, the size and morphology of which are shown in fig. 2 and 3.
Example 12:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 70 wt%, and the molar ratio of C to Ti is 0.6. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, and the TiC particles are regular and nearly octahedral and have uniform sizes.
Example 13:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 40 wt%, and the molar ratio of C to Ti is 0.5. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, and the TiC particles are regular and nearly octahedral and have uniform sizes.
Example 14:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 50 wt%, and the molar ratio of C to Ti is 0.5. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, and the TiC particles are regular and nearly octahedral and have uniform sizes.
Example 15:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 70 wt%, and the molar ratio of C to Ti is 0.5. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, and the TiC particles are regular and nearly octahedral and have uniform sizes.
Example 16:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 40 wt%, and the molar ratio of C to Ti is 0.8. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, and the TiC particles are regular and nearly octahedral and have uniform sizes.
Example 17:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 50 wt%, and the molar ratio of C to Ti is 0.8. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, and the TiC particles are regular and nearly octahedral and have uniform sizes.
Example 18:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 70 wt%, and the molar ratio of C to Ti is 0.8. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, and the TiC particles are regular and nearly octahedral and have uniform sizes.
Comparative example 3:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 70 wt%, and the molar ratio of C to Ti is 0.4. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the TiC particles prepared are extracted from the aluminum matrix using concentrated hydrochloric acid, the morphology of which has begun to shift toward a near-spherical shape.
Comparative example 4:
preparing nanometer polyhedral TiC particles with uniform size and regular shape by combining high temperature and rapid cooling: firstly, Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs are weighed, wherein the Al content is 70 wt%, and the molar ratio of C to Ti is 1.0. And pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of balls to materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 hours.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
The vertical tube furnace was heated to 1400 ℃ with a heating rate of 5 ℃/min. And tying the pressed cylindrical block with molybdenum wires, hanging the cylindrical block into a heating area of a tube furnace from the top of the furnace, keeping the temperature for 14 seconds (the cylindrical block is just ignited), immediately and rapidly cooling the cylindrical block with high-temperature quenching oil, and taking out the product after the cylindrical block is completely cooled.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, and the shape of the TiC particles is nearly spherical.
Further description with respect to the above examples and comparative examples: regarding the temperature range, the temperature for triggering the combustion synthesis reaction of the system is about 880 ℃ to 920 ℃, and in order to enable the reaction to be completed quickly in a short time, the temperature needs to be higher than the critical reaction temperature, so the temperature range is selected from 1000 ℃ to 1600 ℃ reasonably, the general experimental conditions can not be met when the temperature is higher than 1600 ℃, the higher the temperature is selected, the shorter the ignition time is, and the lower the temperature is, the longer the ignition time is.
The invention relates to a preparation method of polyhedral transition metal carbide particles for catalytic materials, which is designed and developed by the invention, the content of aluminum powder and transition metal powder is regulated, high temperature is adopted to combine with rapid cooling to prepare nano transition metal carbide particles, and the pressed block is rapidly cooled at the moment of just igniting, so that the state that the size of the pressed block is uniform and fine (50-100nm) at the initial stage of crystal growth and the appearance is regular is kept. The phenomena of uneven size and irregular appearance caused by continuous growth of the crystal in an uneven temperature field generated in the self-propagating combustion process are avoided, the reaction is sufficient, the preparation process is short, the concentration of defects in the carbide crystal is high, and the catalytic activity is high.
Example 19:
and (3) preparing micrometer polyhedral TiC particles with uniform size and regular shape by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 40 wt%, the molar ratio of C to Ti is 0.6, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, the size is micron grade, and the morphology is near-octahedron.
Example 20:
and (3) preparing micrometer polyhedral TiC particles with uniform size and regular shape by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 60 wt%, the molar ratio of C to Ti is 0.6, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the TiC particles prepared were extracted from the aluminum matrix using concentrated hydrochloric acid, the size and morphology of which are shown in fig. 4.
Example 21:
and (3) preparing micrometer polyhedral TiC particles with uniform size and regular shape by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 70 wt%, the molar ratio of C to Ti is 0.6, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, the size is micron grade, and the morphology is near-octahedron.
Example 22:
and (3) preparing micrometer polyhedral TiC particles with uniform size and regular shape by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 40 wt%, the molar ratio of C to Ti is 0.5, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, the size is micron grade, and the morphology is near-octahedron.
Example 23:
and (3) preparing micrometer polyhedral TiC particles with uniform size and regular shape by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 60 wt%, the molar ratio of C to Ti is 0.5, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, the size is micron grade, and the morphology is near-octahedron.
Example 24:
and (3) preparing micrometer polyhedral TiC particles with uniform size and regular shape by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 70 wt%, the molar ratio of C to Ti is 0.5, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, the size is micron grade, and the morphology is near-octahedron.
Example 25:
and (3) preparing micrometer polyhedral TiC particles with uniform size and regular shape by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 40 wt%, the molar ratio of C to Ti is 0.8, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, the size is micron grade, and the morphology is near-octahedron.
Example 26:
and (3) preparing micrometer polyhedral TiC particles with uniform size and regular shape by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 60 wt%, the molar ratio of C to Ti is 0.8, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, the size is micron grade, and the morphology is near-octahedron.
Example 27:
and (3) preparing micrometer polyhedral TiC particles with uniform size and regular shape by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 70 wt%, the molar ratio of C to Ti is 0.8, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared TiC particles are extracted from the aluminum matrix by using concentrated hydrochloric acid, the size is micron grade, and the morphology is near-octahedron.
Example 28:
and (3) preparing micrometer polyhedral TiC particles with uniform size and regular shape by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 60 wt%, the molar ratio of C to Ti is 0.6, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 15:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 30g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 10 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuously heating to 1600 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out the product, and cooling the product to room temperature in air.
Finally, the TiC particles prepared were extracted from the aluminum matrix using concentrated hydrochloric acid, the size and morphology of which are shown in fig. 5.
Example 29:
and (3) preparing micron polyhedral (Ti, Nb, Zr) C particles with uniform size and regular appearance by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%), Nb powder (the purity is more than or equal to 99.9%), Zr powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 50 wt.%, M is Ti, Nb and Zr are mixed in equal molar ratio, the C/M molar ratio is 0.6, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared (Ti, Nb, Zr) C particles were extracted from the aluminum matrix using concentrated hydrochloric acid, and their size and morphology are shown in fig. 6.
Example 30:
and (3) preparing micron polyhedral (Ti, Nb, Zr) C particles with uniform size and regular appearance by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%), Nb powder (the purity is more than or equal to 99.9%), Zr powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 50 wt.%, M is Ti, Nb and Zr are mixed in equal molar ratio, the C/M molar ratio is 0.5, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared (Ti, Nb, Zr) C particles are extracted from the aluminum matrix by concentrated hydrochloric acid, and the morphology of the particles is regular polyhedron of micrometer.
Example 31:
and (3) preparing micron polyhedral (Ti, Nb, Zr) C particles with uniform size and regular appearance by secondary heating: firstly, weighing Al powder (the purity is more than or equal to 99.9%), Ti powder (the purity is more than or equal to 99.9%), Nb powder (the purity is more than or equal to 99.9%), Zr powder (the purity is more than or equal to 99.9%) and CNTs, wherein the Al content is 50 wt.%, M is Ti, Nb and Zr are mixed in equal molar ratio, the C/M molar ratio is 0.8, pouring the weighed powder into a ball milling tank, and mixing by using a ball mill, wherein the mass ratio of ball materials in the ball milling tank is 10:1, the rotating speed of the ball mill is 50r/min, and the ball milling time is 24 h.
Then, the uniformly mixed powder is sieved out of the ball milling tank, 15g of uniformly mixed powder is weighed and wrapped by aluminum foil, and the uniformly mixed powder is pressed in a self-made grinding tool by a metal compressor to form a cylindrical block with the diameter of 30mm and the height of 5 mm.
And (3) putting the pressed cylindrical block into a vertical tubular furnace, vacuumizing, introducing argon for protection, heating the furnace to 750 ℃, keeping the temperature for 30min, continuing heating to 1400 ℃, keeping the temperature at the heating rate of 5 ℃/min, keeping the temperature for 100min, taking out a product, and cooling the product to room temperature in the air.
Finally, the prepared (Ti, Nb, Zr) C particles are extracted from the aluminum matrix by concentrated hydrochloric acid, and the morphology of the particles is regular polyhedron of micrometer.
The invention relates to a preparation method of polyhedral transition metal carbide particles for catalytic materials, which is designed and developed by the invention, wherein when submicron and micron polyhedral transition metal carbide particles with multiple scales, regular shapes and uniform sizes are prepared by regulating the contents of aluminum powder and transition metal powder and adopting secondary heating, a large amount of nano transition metal carbide particles are formed (can be obtained from embodiment 1) when a prefabricated block is heated to 800 ℃ along with a furnace and is kept warm for 30min, and when the prefabricated block is heated to 1600 ℃ continuously, the heat released by combustion reaction is little, and the whole prefabricated block is in a uniform temperature field, so that the prepared polyhedral carbide particles have uniform sizes and regular shapes; meanwhile, transition metal carbide particles with different sizes can be obtained by keeping the temperature at different temperatures for different times.
Application example 1:
the nano TiC particles prepared in example 11 were used as a catalytic material for hydrogen production from methane, and it was found that the hydrogen production efficiency was improved by 10 times as compared with that of the spherical nanoparticles.
It can be known from examples 1 to 11, comparative examples 1 to 4, and application example 1 that the preparation of nano transition metal carbide particles at medium and low temperatures, the preparation of nano transition metal carbide particles at high temperature combined with rapid cooling, and the preparation of submicron and micron polyhedral transition metal carbide particles by secondary heating provided by the present invention realize a high temperature synthesis process, and the morphology and specific crystal faces of the prepared transition metal carbide are well controlled by regulating the Al content and the M/C ratio, so that the preparation of carbide particles with multi-scale, regular morphology, uniform size, specific crystal faces, and high catalytic activity is realized.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.

Claims (10)

1. A preparation method of polyhedral transition metal carbide particles for catalytic materials is characterized by comprising the following steps:
step 1, uniformly mixing aluminum powder, transition metal powder and a carbon source by ball milling, and pressing into a preparation block;
wherein the transition metal powder comprises titanium powder, tantalum powder, niobium powder, zirconium powder, tungsten powder and/or vanadium powder;
the content of the aluminum powder is 40-70 wt.%, and the molar ratio of the carbon source to the transition metal powder is 0.5-0.8;
step 2, heating the preparation block under the vacuum or argon protection state, cooling to room temperature and taking out;
and 3, soaking with hydrochloric acid to remove the aluminum matrix to obtain polyhedral transition metal carbide particles.
2. The method for preparing polyhedral transition metal carbide granules for catalytic materials as set forth in claim 1, wherein in the step 2, the preparation block is heated to 800 ℃ under vacuum or argon protection, and after 30-90 minutes of heat preservation, cooled to room temperature and taken out.
3. The method as claimed in claim 1, wherein in the step 2, before the preliminary block is heated under vacuum or argon protection, the tubular heating furnace is heated to 1000-1600 ℃ and the temperature is maintained, the preliminary block is covered with molybdenum wires and then hung into the furnace for heat preservation, and after the preliminary block is ignited, the preliminary block is rapidly cooled with high-temperature quenching oil or water.
4. The method as claimed in claim 1, wherein in step 2, the preparation block is heated to 800 ℃ at 700-.
5. The method for preparing polyhedral transition metal carbide granules for catalytic materials according to claim 2, 3 or 4, wherein in the step 1, the mixture is mixed by a ball mill, the ball mass ratio of the ball mill is 5:1-20:1, the rotation speed of the ball mill is 50-100r/min, and the ball milling time is 8-24 h.
6. The method for preparing polyhedral transition metal carbide granules for catalytic materials according to claim 5, wherein the purity of the aluminum powder is more than 99.9% and the purity of the transition metal powder is more than 99.9% in the step 1.
7. The method for preparing polyhedral transition metal carbide granules for catalytic materials according to claim 5, wherein the preliminary blocks are cylindrical in shape and the preliminary blocks are placed in a graphite grinding tool after being formed in step 1.
8. The method for preparing polyhedral transition metal carbide granules for catalytic materials according to claim 7, wherein in the step 1, the carbon source is carbon black or CNTs.
9. The method for preparing polyhedral transition metal carbide granules for catalytic materials according to claim 8, wherein in the step 2, the sintering is performed by a heating furnace, and the heating furnace is a vacuum hot-pressing sintering furnace, a tube furnace or an electromagnetic induction melting furnace.
10. The method for preparing polyhedral transition metal carbide granules for catalytic materials according to claim 9, wherein the heating furnace has a temperature rise rate of 5-30 ℃/min; if the heating is carried out under vacuum, the degree of vacuum should be 10 Pa.
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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3301645A (en) * 1962-04-03 1967-01-31 Exxon Production Research Co Tungsten carbide compositions, method and cutting tool
US3752655A (en) * 1969-02-07 1973-08-14 Nordstjernan Rederi Ab Sintered hard metal product
US5380688A (en) * 1993-08-09 1995-01-10 The Dow Chemical Company Method for making submicrometer carbides, submicrometer solid solution carbides, and the material resulting therefrom
US5746803A (en) * 1996-06-04 1998-05-05 The Dow Chemical Company Metallic-carbide group VIII metal powder and preparation methods thereof
US6190762B1 (en) * 1996-01-15 2001-02-20 Widia Gmbh Composite body and method of producing the same
US20010029232A1 (en) * 1997-07-27 2001-10-11 Moris Eisen Process for the production of stereoregular polymers and elastomers of alpha-olefins and certain novel catalysts therefor
US20060051281A1 (en) * 2004-09-09 2006-03-09 Bhabendra Pradhan Metal carbides and process for producing same
CN1751990A (en) * 2005-11-03 2006-03-29 武汉科技大学 Preparation method of transition metal carbide material
US20070032369A1 (en) * 2005-08-03 2007-02-08 Franzen Jan M High content CBN materials, compact incorporating the same and methods of making the same
CN104195364A (en) * 2014-09-12 2014-12-10 攀枝花学院 Titanium-based metal carbide and preparation method thereof
EP3098199A1 (en) * 2015-05-26 2016-11-30 Fabbrica Italiana Leghe Metalliche Sinterizzate (F.I.L.M.S.) S.p.A. Process for the direct production of tungsten carbide powders of various grain sizes starting from scheelite
CN108083278A (en) * 2017-12-26 2018-05-29 佛山科学技术学院 A kind of titanium aluminium tin carbon-coating shape solid solution powder and preparation method thereof
CN108584958A (en) * 2018-05-09 2018-09-28 台州学院 A kind of in-situ synthetic method of zirconium carbide nano-powder
US20180290933A1 (en) * 2015-01-22 2018-10-11 University Of Utah Research Foundation Functionally graded carbides
CN110484796A (en) * 2019-09-20 2019-11-22 吉林大学 A kind of high entropy ceramic particle of transition metal carbide and preparation method thereof
CN111101074A (en) * 2018-10-26 2020-05-05 青海民族大学 In-situ carbide particle-embedded 3D amorphous alloy network reinforced boron steel-based composite material and preparation method thereof

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3301645A (en) * 1962-04-03 1967-01-31 Exxon Production Research Co Tungsten carbide compositions, method and cutting tool
US3752655A (en) * 1969-02-07 1973-08-14 Nordstjernan Rederi Ab Sintered hard metal product
US5380688A (en) * 1993-08-09 1995-01-10 The Dow Chemical Company Method for making submicrometer carbides, submicrometer solid solution carbides, and the material resulting therefrom
US6190762B1 (en) * 1996-01-15 2001-02-20 Widia Gmbh Composite body and method of producing the same
US5746803A (en) * 1996-06-04 1998-05-05 The Dow Chemical Company Metallic-carbide group VIII metal powder and preparation methods thereof
KR20000016327A (en) * 1996-06-04 2000-03-25 오엠지 아메리카스, 인코포레이티드 Metallic carbide-group viii metal powder and its preparation
US20010029232A1 (en) * 1997-07-27 2001-10-11 Moris Eisen Process for the production of stereoregular polymers and elastomers of alpha-olefins and certain novel catalysts therefor
US20060051281A1 (en) * 2004-09-09 2006-03-09 Bhabendra Pradhan Metal carbides and process for producing same
US20070032369A1 (en) * 2005-08-03 2007-02-08 Franzen Jan M High content CBN materials, compact incorporating the same and methods of making the same
CN1751990A (en) * 2005-11-03 2006-03-29 武汉科技大学 Preparation method of transition metal carbide material
CN104195364A (en) * 2014-09-12 2014-12-10 攀枝花学院 Titanium-based metal carbide and preparation method thereof
US20180290933A1 (en) * 2015-01-22 2018-10-11 University Of Utah Research Foundation Functionally graded carbides
EP3098199A1 (en) * 2015-05-26 2016-11-30 Fabbrica Italiana Leghe Metalliche Sinterizzate (F.I.L.M.S.) S.p.A. Process for the direct production of tungsten carbide powders of various grain sizes starting from scheelite
CN108083278A (en) * 2017-12-26 2018-05-29 佛山科学技术学院 A kind of titanium aluminium tin carbon-coating shape solid solution powder and preparation method thereof
CN108584958A (en) * 2018-05-09 2018-09-28 台州学院 A kind of in-situ synthetic method of zirconium carbide nano-powder
CN111101074A (en) * 2018-10-26 2020-05-05 青海民族大学 In-situ carbide particle-embedded 3D amorphous alloy network reinforced boron steel-based composite material and preparation method thereof
CN110484796A (en) * 2019-09-20 2019-11-22 吉林大学 A kind of high entropy ceramic particle of transition metal carbide and preparation method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
SHENBAO JIN ET AL: ""A common regularity of stoichiometry-induced morphology evolution of transition metal carbides, nitrides, and diborides during self-propagating high-temperature synthesis"", 《CRYSTAL GROWTH & DESIGN》 *
SHENBAO JIN ET AL: "Self-propagating high-temperature synthesis of nano-TiCx particles with different shapes by using carbon nano-tube as C source", 《NANOSCALE RESEARCH LETTERS》 *
王瑞红等: "《类铂材料在燃料电池中的应用及其与贵金属的协同效应》", 30 June 2017, 黑龙江大学出版社 *
谢真等: "真空原位碳热还原法制备纳米碳化钛粉体", 《钢铁钒钛》 *
陈佑剑: ""常见过渡金属碳化物的制备及其性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

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