CN116969454A - Batch preparation method of graphene-diamond covalent heterostructure particles - Google Patents
Batch preparation method of graphene-diamond covalent heterostructure particles Download PDFInfo
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- 239000010432 diamond Substances 0.000 title claims abstract description 174
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 174
- 239000002245 particle Substances 0.000 title claims abstract description 170
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 44
- 229910052733 gallium Inorganic materials 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 8
- 238000001764 infiltration Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 230000001413 cellular effect Effects 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 10
- 239000000725 suspension Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000010453 quartz Substances 0.000 description 14
- 238000001237 Raman spectrum Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
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- 238000001514 detection method Methods 0.000 description 7
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- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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Abstract
According to the batch preparation method of the graphene-diamond covalent heterostructure particles, liquid metal catalysts are subjected to micro-droplet formation, meanwhile, diamond particles are uniformly wrapped on the surfaces of the micro-droplets and forcedly infiltrated, so that the diamond particles and the catalyst micro-droplets form honeycomb distribution, batch diamond particles are enabled to be infiltrated in a suspension manner among the catalyst micro-droplets, and then graphene sheets with covalent bond interface bonding are grown on the diamond surfaces through heating. The method can realize the graphene coverage rate of 80% -90% on average of all surfaces of the diamond particles above gram level, and the catalyst recycling rate reaches above 97%, thereby providing important technical support for batch preparation of the graphene-diamond covalent heterostructure particles.
Description
Technical Field
The invention relates to a technology in the field of diamond preparation, in particular to a batch preparation method of graphene-diamond covalent heterostructure particles.
Background
The diamond and the graphene are allotropes and have extremely excellent performances, and the two are combined through covalent bonds to form a graphene-diamond covalent heterostructure, so that the respective performance advantages of the diamond and the graphene can be fully exerted, and the graphene-diamond covalent heterostructure has extremely excellent mechanical, thermal and electrical performances. The preparation of the graphene-diamond composite material with high performance is expected to be realized by preparing graphene-diamond covalent heterostructure particles and performing bulk material molding. However, the existing preparation method of graphene-diamond covalent heterostructures catalyzed by low-melting-point metals can only realize graphene growth on the surfaces of very few diamond particles, thereby preventing industrial application of the novel carbon nanomaterial.
Disclosure of Invention
Aiming at the defect that the preparation of graphene on the surfaces of diamond particles with multiple surfaces and multiple points cannot be realized in the prior art, the invention provides a batch preparation method of graphene-diamond covalent heterostructure particles, and the graphene coverage rate of 80% -90% on average of all the surfaces of the diamond particles with the gram grade or above can be realized by technical means such as micro-droplet formation of a liquid metal catalyst and honeycomb suspension infiltration of the diamond particles, and the catalyst recycling rate reaches more than 97%, so that important technical support is provided for batch preparation of the graphene-diamond covalent heterostructure particles.
The invention is realized by the following technical scheme:
the invention relates to a batch preparation method of graphene-diamond covalent heterostructure particles, which comprises the steps of uniformly wrapping diamond particles on the surfaces of micro-droplets while carrying out micro-droplet formation on a liquid metal catalyst, and carrying out forced infiltration, so that the diamond particles and the catalyst micro-droplets form honeycomb distribution, the batch diamond particles are caused to suspend and infiltrate among the catalyst micro-droplets, and then a graphene sheet layer with covalent bond interface bonding grows on the diamond surface by heating.
The diamond particles may be, but are not limited to, monocrystalline diamond particles, polycrystalline diamond particles, boron doped diamond particles, or combinations thereof.
The liquid metal catalyst is simple substance gallium.
The micro-droplet formation refers to: the liquid metal catalyst is divided into droplets of 10-1000 μm in size by, but not limited to, knife cutting, laser cutting, microporous mesh cutting, etc.
The diameter of the micro liquid drop is 10-100 times of the diameter of the diamond particle.
The uniform coating refers to: the liquid metal is divided and coated with diamond particles, so that the phenomenon that the liquid metal newly-grown surface forms an oxide film and cannot be bonded with the diamond particles is avoided.
The uniform coating is preferably carried out by coating only one layer of diamond particles on all areas of the surface of the liquid metal catalyst micro-droplets.
The forced infiltration means: pressure is applied from the upper part of the metal micro-droplet to realize forced infiltration between the diamond particles and the liquid metal catalyst, specifically: external pressure is applied above a container filled with the mixture of the liquid metal catalyst and the diamond particles through a balancing weight, so that the catalyst and the surfaces of the diamond particles form multi-surface close contact.
The honeycomb distribution refers to: the catalyst microdroplets with the diamond particles coated on the surfaces are mutually stacked and extruded to form a honeycomb structure with the catalyst microdroplets as a nest core and the diamond particles as nest edges, so that batches of diamond particles are suspended among the catalyst microdroplets.
The pressure value of the external pressure is 500-10000Pa.
The heating means: heating the mixture of the liquid metal catalyst and the diamond particles to 1000-1200 ℃ by adopting a reaction furnace under vacuum condition or auxiliary carbon source condition, and reacting for 15-60min.
The reaction furnace adopts, but is not limited to, a vacuum heating furnace such as a CVD tube furnace and the like.
The vacuum condition is that the air pressure is less than 1Pa.
The auxiliary carbon source adopts, but is not limited to, methane, acetone and the like, and the flow rate of the auxiliary carbon source is 5-50sccm, and the corresponding hydrogen flow rate is 50-200sccm.
The heating is preferably performed by preheating a heating furnace, and then placing the sample in a preheating zone for rapid heating, wherein the actual heating rate is 50-100 ℃/min.
Preferably, after the heating reaction is finished, the sample is placed in a diluted acid solution for ultrasonic treatment, the liquid metal catalyst is recovered, and collection of graphene-diamond covalent heterostructure particles is achieved through suction filtration.
The diluted acid solution comprises, but is not limited to, 10-20% by mass of HCl and H 2 SO 2 The temperature of the solution is 40-80 ℃.
The ultrasonic power of the ultrasonic treatment is 240-720W, and the ultrasonic treatment time is 1-5min.
The method is characterized in that after the ultrasonic treatment is finished, the original liquid metal catalyst microdroplets are recombined into a whole, and the liquid metal is solidified by cooling and then recycled.
The cooling refers to cooling the liquid metal to below the solidification temperature, and the cooling mode includes but is not limited to water bath cooling, air cooling and the like.
The collection refers to the collection of graphene-diamond heterostructure particles dissolved in dilute acid after the recovery of the liquid metal catalyst, including but not limited to the collection of particles by a microporous filter membrane and a suction filtration device.
The invention relates to graphene-diamond covalent heterostructure particles prepared by the method, which comprises the following steps: the diamond particles and a plurality of graphene sheets uniformly and vertically covered on the surfaces of the diamond particles, wherein the graphene sheets are connected with the diamond through covalent bonds.
The height of the graphene sheet layer is 500-1200nm.
Technical effects
According to the invention, the liquid metal catalyst is subjected to micro-droplet formation and coated with diamond particles, a honeycomb structure with the catalyst micro-droplets as a nest core and the diamond particles as nest edges is formed under external pressure, so that batch diamond is suspended among the catalyst micro-droplets, and multi-surface contact is formed. Compared with the prior art, the preparation method can realize multi-surface contact of batch diamond particles and the liquid metal catalyst, and further realize preparation of batch graphene-diamond covalent heterostructure particles. The technical means thoroughly solves the technical problem that the multi-level, multi-point and multi-surface catalytic growth of the graphene on the diamond particles cannot be realized by adopting the liquid metal catalyst. The technical means has the technical condition of directly and industrially producing graphene-diamond covalent heterostructure particles in batches, the conversion rate of the graphene-diamond covalent heterostructure particles produced in batches can be increased from less than 1% to 80% -90% of the prior art means, and the catalyst recycling rate can reach 97%.
Drawings
FIG. 1 is a schematic diagram of the present invention;
FIG. 2 is a scanning electron microscope, raman spectrum and heterostructure interface transmission electron microscope image of a reaction of graphene-diamond covalent heterostructure particles of 10-20 microns for 15 min;
FIG. 3 is a scanning electron microscope of a reaction of 10-20 μm graphene-diamond covalent heterostructure particles for 30 min;
FIG. 4 is a Raman spectrum of a 10-20 micron graphene-diamond covalent heterostructure particle reacted for 30 minutes;
FIG. 5 is a macroscopic photograph of a 10-20 micron graphene-diamond covalent heterostructure particle reaction for 30 minutes;
FIG. 6 is an XRD pattern of a graphene-diamond covalent heterostructure particle of 10-20 microns before and after 30min of reaction
FIG. 7 is a Raman Mapping of a 10-20 micron graphene-diamond covalent heterostructure particle reaction for 30min
FIG. 8 is a scanning electron microscope of a reaction of 10-20 μm graphene-diamond covalent heterostructure particles for 60min;
FIG. 9 is a Raman spectrum of a 10-20 micron graphene-diamond covalent heterostructure particle reaction for 60 minutes;
FIG. 10 is a scanning electron microscope of 2-3 micron graphene-diamond covalent heterostructure particle reaction for 60min;
FIG. 11 is a scanning electron microscope of 5-6 microns boron doped graphene-diamond covalent heterostructure particles reacted for 30 min;
FIG. 12 is a scanning electron microscope of 2-3 microns boron doped graphene-diamond covalent heterostructure particles reacted for 30 min;
FIG. 13 is an XRD pattern of 2-3 microns of boron doped graphene-diamond covalent heterostructure particles before and after 30 minutes of reaction;
FIG. 14 is a Raman Mapping of 2-3 micron boron doped graphene-diamond covalent heterostructure particles reacted for 30 min.
Detailed Description
Example 1
The preparation method of the graphene-diamond covalent heterostructure particles with the particle size of 10-20 microns comprises the following steps:
step 1, as shown in fig. 1, a cutter is used to divide liquid gallium into a plurality of micro-droplets, and diamond particles are wrapped when each micro-droplet is generated, so that the micro-droplet polymerization is avoided.
And 2, continuously rolling the gallium micro-droplets to uniformly mix the gallium micro-droplets with the surfaces of the diamond particles, and removing redundant diamond particles in a vibration mode, so that each micro-droplet surface is only coated with one layer of diamond particles.
And 3, placing the micro-droplets coated with the diamond particles into a quartz container, and adding a quartz balancing weight above the micro-droplets.
And 4, placing the sample in a preheated CVD tube furnace, quickly heating the sample to 1050 ℃, reacting for 15min, and quickly cooling the sample to room temperature after the reaction is finished.
And 5, taking out a sample, and placing the sample in an HCl solution with the mass fraction of 10% (the temperature is 40 ℃).
And 6, performing ultrasonic treatment for 1min by adopting 480W power to separate graphene-diamond heterostructure particles from gallium, and enabling gallium microdroplets to be recombined into a whole, and taking out and recycling the gallium after cooling.
And 7, adopting a microporous filter membrane with the aperture of 0.2 micron to carry out suction filtration and collection on graphene-diamond covalent heterostructure particles dissolved in 10% HCl solution, and drying.
The detection by a scanning electron microscope shows that a plurality of graphene sheets grow on the surface of the diamond particle at the moment, the height of the graphene sheets is low (100-200 nm), the graphene sheets are in a nucleation stage, the graphene sheets are mixed into single-layer graphene, double-layer graphene and few-layer graphene through Raman spectrum analysis, and the graphene sheets are in covalent bond connection through transmission electron microscope interface analysis, as shown in figure 2.
Example 2
The preparation method of the graphene-diamond covalent heterostructure particles with the particle size of 10-20 microns comprises the following steps:
step 1, as shown in fig. 1, a cutter is used to divide liquid gallium into a plurality of micro-droplets, and diamond particles are wrapped when each micro-droplet is generated, so that the micro-droplet polymerization is avoided.
And 2, continuously rolling the gallium micro-droplets to uniformly mix the gallium micro-droplets with the surfaces of the diamond particles, and removing redundant diamond particles in a vibration mode, so that each micro-droplet surface is only coated with one layer of diamond particles.
And 3, placing the micro-droplets coated with the diamond particles into a quartz container, and adding a quartz balancing weight above the micro-droplets.
And 4, placing the sample in a preheated CVD tube furnace, quickly heating the sample to 1050 ℃, reacting for 30min, and quickly cooling the sample to room temperature after the reaction is finished.
And 5, taking out a sample, and placing the sample in an HCl solution with the mass fraction of 10% (the temperature is 40 ℃).
And 6, performing ultrasonic treatment for 2min by adopting 480W power to separate graphene-diamond heterostructure particles from gallium, and enabling gallium microdroplets to be recombined into a whole, and taking out and recycling the gallium after cooling.
And 7, adopting a microporous filter membrane with the aperture of 0.2 micron to carry out suction filtration and collection on graphene-diamond covalent heterostructure particles dissolved in 10% HCl solution, and drying.
The detection by a scanning electron microscope is shown in fig. 3, the surface of the diamond particle is uniformly covered with a plurality of graphene sheets, the height is 500-1000nm, the average coverage rate is about 90% by statistics, and the graphene is a single-layer graphene, a double-layer graphene and a few-layer graphene mixture by Raman spectrum analysis is shown in fig. 4. The color of the prepared particles was significantly blackened as compared to pure diamond particles as shown in fig. 5. The graphene coating on the surface of the diamond particles is remarkable in batch quantity as shown by XRD analysis of 1 gram of powder (figure 6), and is high in coverage rate and mainly thin in layer number as shown by Raman spectrum Mapping analysis after reaction (figure 7).
Example 3
The preparation method of the graphene-diamond covalent heterostructure particles with the particle size of 10-20 microns comprises the following steps:
step 1, as shown in fig. 1, a cutter is used to divide liquid gallium into a plurality of micro-droplets, and diamond particles are wrapped when each micro-droplet is generated, so that the micro-droplet polymerization is avoided.
And 2, continuously rolling the gallium micro-droplets to uniformly mix the gallium micro-droplets with the surfaces of the diamond particles, and removing redundant diamond particles in a vibration mode, so that each micro-droplet surface is only coated with one layer of diamond particles.
And 3, placing the micro-droplets coated with the diamond particles into a quartz container, and adding a quartz balancing weight above the micro-droplets.
And 4, placing the sample in a preheated CVD tube furnace, quickly heating the sample to 1050 ℃, reacting for 60min, and quickly cooling the sample to room temperature after the reaction is finished.
And 5, taking out a sample, and placing the sample in an HCl solution with the mass fraction of 10% (the temperature is 40 ℃).
And carrying out ultrasonic treatment for 5min by adopting 720W power to separate graphene-diamond heterostructure particles from gallium, and enabling gallium microdroplets to be recombined into a whole, and taking out and recycling the gallium after cooling.
And 7, adopting a microporous filter membrane with the aperture of 0.2 micron to carry out suction filtration and collection on graphene-diamond covalent heterostructure particles dissolved in 10% HCl solution, and drying.
The detection shows that a plurality of graphene sheets are uniformly covered on the surface of the diamond particles at the moment through a scanning electron microscope as shown in fig. 8, the height is 800-1200nm, the average coverage rate is about 87% through statistics, and the graphene is a single-layer graphene, a double-layer graphene and a few-layer graphene mixture through Raman spectrum analysis as shown in fig. 9.
Example 4
The preparation method of the graphene-diamond covalent heterostructure particles with the particle size of 5-10 microns comprises the following steps:
step 1, as shown in fig. 1, a cutter is used to divide liquid gallium into a plurality of micro-droplets, and diamond particles are wrapped when each micro-droplet is generated, so that the micro-droplet polymerization is avoided.
And 2, continuously rolling the gallium micro-droplets to uniformly mix the gallium micro-droplets with the surfaces of the diamond particles, and removing redundant diamond particles in a vibration mode, so that each micro-droplet surface is only coated with one layer of diamond particles.
And 3, placing the micro-droplets coated with the diamond particles into a quartz container, and adding a quartz balancing weight above the micro-droplets.
And 4, placing the sample in a preheated CVD tube furnace, quickly heating the sample to 1050 ℃, reacting for 30min, and quickly cooling the sample to room temperature after the reaction is finished.
And 5, taking out a sample, and placing the sample in an HCl solution with the mass fraction of 10% (the temperature is 40 ℃).
And 6, performing ultrasonic treatment for 2min by adopting 480W power to separate graphene-diamond heterostructure particles from gallium, and enabling gallium microdroplets to be recombined into a whole, and taking out and recycling the gallium after cooling.
And 6, etching the silicon oxide in a closed container for 3 hours at 50 ℃ by adopting 40% hydrofluoric acid.
And 7, adopting a microporous filter membrane with the aperture of 0.2 micron to carry out suction filtration and collection on graphene-diamond covalent heterostructure particles dissolved in 10% HCl solution, and drying.
The detection by a scanning electron microscope shows that a plurality of graphene sheets are uniformly covered on the surface of the diamond particles, the height is 600-1000nm, the average coverage rate is about 80% by statistics, and the graphene is the mixture of single-layer, double-layer and few-layer graphene through Raman spectrum analysis.
Example 5
2-3 microns of graphene-diamond covalent heterostructure particles, comprising the steps of:
step 1, as shown in fig. 1, a cutter is used to divide liquid gallium into a plurality of micro-droplets, and diamond particles are wrapped when each micro-droplet is generated, so that the micro-droplet polymerization is avoided.
And 2, continuously rolling the gallium micro-droplets to uniformly mix the gallium micro-droplets with the surfaces of the diamond particles, and removing redundant diamond particles in a vibration mode, so that each micro-droplet surface is only coated with one layer of diamond particles.
And 3, placing the micro-droplets coated with the diamond particles into a quartz container, and adding a quartz balancing weight above the micro-droplets.
And 4, placing the sample in a preheated CVD tube furnace, quickly heating the sample to 1000 ℃, reacting for 30min, and quickly cooling the sample to room temperature after the reaction is finished.
And 5, taking out a sample, and placing the sample in an HCl solution with the mass fraction of 15% (the temperature is 40 ℃).
And 6, performing ultrasonic treatment for 2min by adopting 480W power to separate graphene-diamond heterostructure particles from gallium, and enabling gallium microdroplets to be recombined into a whole, and taking out and recycling the gallium after cooling.
And 7, adopting a microporous filter membrane with the aperture of 0.2 micron to carry out suction filtration and collection on graphene-diamond covalent heterostructure particles dissolved in 10% HCl solution, and drying.
As shown in FIG. 10, the detection shows that the diamond particles are uniformly covered with a plurality of graphene sheets, the height is 500-800nm, the average coverage rate is about 90% by statistics, and the graphene is a mixture of single-layer graphene, double-layer graphene and few-layer graphene by Raman spectrum analysis.
Example 6
The preparation method of the boron doped graphene-diamond covalent heterostructure particles with the particle size of 5-6 microns comprises the following steps:
step 1, as shown in fig. 1, a cutter is used to divide liquid gallium into a plurality of micro-droplets, and diamond particles are wrapped when each micro-droplet is generated, so that the micro-droplet polymerization is avoided.
And 2, continuously rolling the gallium micro-droplets to uniformly mix the gallium micro-droplets with the surfaces of the diamond particles, and removing redundant diamond particles in a vibration mode, so that each micro-droplet surface is only coated with one layer of diamond particles.
And 3, placing the micro-droplets coated with the diamond particles into a quartz container, and adding a quartz balancing weight above the micro-droplets.
And 4, placing the sample in a preheated CVD tube furnace, quickly heating the sample to 1050 ℃, reacting for 30min, and quickly cooling the sample to room temperature after the reaction is finished.
And 5, taking out a sample, and placing the sample in an HCl solution with the mass fraction of 10% (the temperature is 40 ℃).
And 6, performing ultrasonic treatment for 1min by adopting 480W power to separate graphene-diamond heterostructure particles from gallium, and enabling gallium microdroplets to be recombined into a whole, and taking out and recycling the gallium after cooling.
And 7, adopting a microporous filter membrane with the aperture of 0.2 micron to carry out suction filtration and collection on graphene-diamond covalent heterostructure particles dissolved in 10% HCl solution, and drying.
As shown in FIG. 11, the detection shows that the diamond particles are uniformly covered with a plurality of graphene sheets, the height is 500-1000nm, the average coverage rate is about 80% by statistics, and the graphene is a mixture of single-layer graphene, double-layer graphene and few-layer graphene through Raman spectrum analysis.
Example 7
2-3 microns of boron doped graphene-diamond covalent heterostructure particles, comprising the following steps:
and uniformly mixing silicon oxide particles with similar particle sizes with the diamond particles in a mass ratio of 2:1 in a mechanical mixing or liquid phase mixing mode.
Step 1, as shown in fig. 1, a cutter is used to divide liquid gallium into a plurality of micro-droplets, and each micro-droplet is generated and coated with oxidized diamond particles, so that the micro-droplet polymerization is avoided.
And 2, continuously rolling the gallium micro-droplets to uniformly mix the gallium micro-droplets with the surfaces of the diamond particles, and removing redundant diamond particles in a vibration mode, so that each micro-droplet surface is only coated with one layer of diamond particles.
And 3, placing the micro-droplets coated with the diamond particles into a quartz container, and adding a quartz balancing weight above the micro-droplets.
And 4, placing the sample in a preheated CVD tube furnace, quickly heating the sample to 1050 ℃, reacting for 30min, and quickly cooling the sample to room temperature after the reaction is finished.
And 5, taking out a sample, and placing the sample in an HCl solution with the mass fraction of 10% (the temperature is 40 ℃).
And 6, performing ultrasonic treatment for 1min by adopting 480W power to separate graphene-diamond heterostructure particles from gallium, and enabling gallium microdroplets to be recombined into a whole, and taking out and recycling the gallium after cooling.
And 7, adopting a microporous filter membrane with the aperture of 0.2 micron to carry out suction filtration and collection on graphene-diamond covalent heterostructure particles dissolved in 10% HCl solution, and drying.
As shown in FIG. 12, the detection shows that the diamond particles are uniformly covered with a plurality of graphene sheets, the height is 500-1000nm, the average coverage rate is about 80-90% by statistics, and the graphene is a mixture of single-layer graphene, double-layer graphene and few-layer graphene by Raman spectrum analysis. As shown in fig. 13, the graphene coating on the surface of the diamond particles was found to be significant in batch size by XRD analysis of 1 g of powder, and the graphene coating on the surface of the diamond particles was found to be high in coverage by raman spectrum Mapping analysis after the reaction, and the number of layers was mainly thin, as shown in fig. 14.
Compared with the prior art, the method has the advantages that the liquid metal catalyst is micro-dripped and coated with the diamond particles, and the diamond particles and the catalyst micro-dripped form honeycomb suspension infiltration under the external pressure condition, so that batch diamond particles are contacted with multiple surfaces of the liquid metal catalyst, and finally, the conversion rate of graphene-diamond covalent heterostructure particles prepared by the prior art is less than 1% to 80% -90%, so that the technical requirement of industrial mass production can be met.
The foregoing embodiments may be partially modified in numerous ways by those skilled in the art without departing from the principles and spirit of the invention, the scope of which is defined in the claims and not by the foregoing embodiments, and all such implementations are within the scope of the invention.
Claims (10)
1. The preparation method of the graphene-diamond covalent heterostructure particles is characterized in that liquid metal catalysts are subjected to micro-droplet formation, diamond particles are uniformly wrapped on the surfaces of the micro-droplets and are subjected to forced infiltration, so that the diamond particles and the catalyst micro-droplets form honeycomb distribution, batch diamond particles are caused to suspend and infiltrate among the catalyst micro-droplets, and then graphene sheets with covalent bond interface bonding are grown on the diamond surfaces through heating;
the liquid metal catalyst is simple substance gallium.
2. The method of claim 1, wherein the diamond particles are monocrystalline diamond particles, polycrystalline diamond particles, boron doped diamond particles, or a combination thereof.
3. The method for batch preparation of graphene-diamond covalent heterostructure particles according to claim 1, wherein the micro-droplet formation means: dividing the liquid metal catalyst into droplets with the size of 10-1000 mu m;
the diameter of the micro liquid drop is 10-100 times of the diameter of the diamond particle.
4. The method for batch preparation of graphene-diamond covalent heterostructure particles according to claim 1, wherein the uniform coating is: the liquid metal is divided and coated with diamond particles, so that the phenomenon that the liquid metal newly-grown surface forms an oxide film and cannot be bonded with the diamond particles is avoided.
5. The method for preparing graphene-diamond covalent heterostructure particles in batches according to claim 1, wherein the uniform coating is carried out by coating only one layer of diamond particles on all areas of the surface of the liquid metal catalyst micro-droplet.
6. The method for preparing graphene-diamond covalent heterostructure particles in batches according to claim 1, wherein the forced infiltration means: pressure is applied from the upper part of the metal micro-droplet to realize forced infiltration between the diamond particles and the liquid metal catalyst, specifically: external pressure is applied above a container filled with the mixture of the liquid metal catalyst and the diamond particles through a balancing weight, so that the catalyst and the surfaces of the diamond particles form multi-surface close contact.
7. The method for batch preparation of graphene-diamond covalent heterostructure particles according to claim 1, wherein the cellular distribution is: the catalyst microdroplets with the diamond particles coated on the surfaces are mutually stacked and extruded to form a honeycomb structure with the catalyst microdroplets as a nest core and the diamond particles as nest edges, so that batches of diamond particles are suspended among the catalyst microdroplets.
8. The method for batch preparation of graphene-diamond covalent heterostructure particles according to claim 1, wherein the heating means: heating the mixture of the liquid metal catalyst and the diamond particles to 1000-1200 ℃ by adopting a reaction furnace under vacuum condition or auxiliary carbon source condition, and reacting for 15-60min;
the heating is as follows: firstly preheating a heating furnace, and then placing the sample in a preheating zone for rapid heating, wherein the actual heating rate is 50-100 ℃/min.
9. The method for preparing graphene-diamond covalent heterostructure particles in batches according to claim 1, wherein the step of recovering the liquid metal catalyst is to recover and recycle the liquid metal after the completion of ultrasonic treatment by re-agglomerating the original liquid metal catalyst microdroplets into a whole and cooling.
10. A graphene-diamond covalent heterostructure particle prepared based on the preparation method of any one of claims 1 to 9, comprising: the diamond particles and a plurality of graphene sheets uniformly and vertically covered on the surfaces of the diamond particles, wherein the graphene sheets are connected with the diamond through covalent bonds;
the height of the graphene sheet layer is 500-1200nm.
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