CN117504764A - Device and method for preparing doped graphene - Google Patents
Device and method for preparing doped graphene Download PDFInfo
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- CN117504764A CN117504764A CN202311509698.5A CN202311509698A CN117504764A CN 117504764 A CN117504764 A CN 117504764A CN 202311509698 A CN202311509698 A CN 202311509698A CN 117504764 A CN117504764 A CN 117504764A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 174
- 238000000034 method Methods 0.000 title claims abstract description 32
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- 239000007787 solid Substances 0.000 claims abstract description 80
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- 239000002184 metal Substances 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 65
- 239000012159 carrier gas Substances 0.000 claims abstract description 34
- 238000005276 aerator Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims description 127
- 238000010438 heat treatment Methods 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 45
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- 150000002431 hydrogen Chemical class 0.000 claims description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 29
- 238000011084 recovery Methods 0.000 claims description 28
- 238000006555 catalytic reaction Methods 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
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- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
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- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 230000001276 controlling effect Effects 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
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- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
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- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
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- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/006—Baffles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a device and a method for preparing doped graphene. According to the invention, the carbon source, the doping gaseous source or the doping solid source and the carrier gas are formed into bubbles through the aerator and are introduced into the molten metal, and the single-element or multi-element doped graphene is obtained by adjusting the type and concentration of the doping gas or the type and weight of the solid, so that a means for effectively preparing the doped graphene is provided for the prior art. The method can prepare the graphene doped in situ, does not need to add a catalyst, effectively simplifies the production process of the doped graphene, and can continuously prepare the graphene material doped with single element or co-doped with multiple elements by a one-step method. The doping source can be gas or solid, so that the doping range is enlarged, multiple elements can be doped simultaneously, the number of layers of the doped graphene is adjustable, and the doping elements and the doping concentration are easy to control. The method is simple and feasible, has high efficiency, uniform doping and high stability, and can be used for large-scale production.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to a device and a method for preparing doped graphene.
Background
Graphene is a two-dimensional material composed of a single layer of carbon atoms, and has excellent conductivity, high strength and flexibility. There has been increasing interest in successfully separating graphene from graphite in the laboratory by multiple "tape tears" by the physicists anderson and Constant no Wo Xiao love at the university of Manchester, UK. However, the graphene material with a single component has certain limitations, such as easy agglomeration, difficult processing and forming, and the like, so that the application of the graphene is greatly limited. Graphene doping, however, can increase carrier concentration and change the fermi level position of graphene, has become an important way to expand its application.
The patent application CN116354341A, CN116443866A and the like all need to prepare graphene firstly, and then mix doping gas or doping substances with the prepared graphene in advance, so that the preparation efficiency is low. The patent CN104045075 adopts a chemical vapor deposition method to prepare the doped graphene, and the prepared graphene film needs to be transferred again, so that the process is complicated and is not beneficial to continuous preparation.
Disclosure of Invention
In view of this, the present invention provides a method of preparing doped graphene. According to the method provided by the invention, the catalyst is additionally added, so that the production process of the doped graphene is effectively simplified, the production efficiency is improved, the production cost is reduced, and the single-element doped or multi-element co-doped graphene material can be continuously prepared by a one-step method.
The invention provides a device for preparing doped graphene, which comprises:
a gas mixing device 1;
a solid source bin 2 with an air inlet communicated with an air outlet of the air mixing device 1;
a reaction furnace 3 with a feed inlet communicated with a discharge outlet of the solid source bin 2; wherein, a flowmeter 4 and an aerator 5 are also arranged on the connecting pipeline between the solid source bin 2 and the reaction furnace 3;
the collecting device 6 is communicated with the discharge port of the reaction furnace 3;
a gas recovery device 7 with a gas inlet communicated with the gas outlet of the collection device 6;
wherein,
a heating system 2-1 and a material tray 2-2 are arranged in the solid source bin 2; the heating system 2-1 is also connected with a temperature control device 2-3.
Preferably, a graphene filter is disposed in the collecting device 6.
The invention also provides a method for preparing the doped graphene, which is prepared by using the device for preparing the doped graphene in the technical scheme; the preparation process comprises the following steps:
a) Placing a metal catalyst in a reaction furnace 3, and performing gas replacement on the reaction furnace 3 to form an inert atmosphere in the reaction furnace; then heating the reaction furnace 3 to melt the metal catalyst to form molten metal;
b) Carrying out step b 1), b 2) or b 3):
b1 Introducing a carbon-containing gas, a carrier gas and a doping gaseous source into a gas mixing device 1 to be mixed to form a mixed gas, controlling the flow of the mixed gas through a flowmeter 4, introducing the mixed gas into a reaction furnace 3 from the bottom of the reaction furnace 3 to contact with molten metal in the reaction furnace 3 after aeration treatment by an aerator 5, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene;
or (b)
b2 Introducing carbon-containing gas and carrier gas into a gas mixing device 1 to be mixed to form mixed gas, opening a heating system 2-1 in a solid source bin 2 to heat a doped solid source in a charging tray 2-2, controlling the flow of the mixed gas through the heated solid source by a flowmeter 4, introducing the mixed gas into a reaction furnace 3 from the bottom of the reaction furnace 3 to be contacted with molten metal in the reaction furnace 3 after aeration treatment by an aerator 5, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene;
or (b)
b3 Introducing carbon-containing gas, carrier gas and doping gaseous source into a gas mixing device 1 to be mixed to form mixed gas, opening a heating system 2-1 in a solid source bin 2 to heat the doping solid source in a material tray 2-2, controlling the flow of the mixed gas through the heated solid source by a flowmeter 4, introducing the mixed gas into a reaction furnace 3 from the bottom of the reaction furnace 3 to be contacted with molten metal in the reaction furnace 3 after aeration treatment by an aerator 5, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene;
c) The doped graphene enters a collecting device 6 along with hydrogen, and the doped graphene is collected in the collecting device 6 to obtain a doped graphene product; the hydrogen gas continues to enter the gas recovery device 7 for recovery.
Preferably, the metal catalyst is at least one of iron, cobalt, nickel, copper, chromium, gold, silver, platinum, zinc, aluminum, chromium, manganese, titanium, tin, magnesium, gallium, indium, and palladium.
Preferably, in step a), the heating temperature is 900 to 1700 ℃.
Preferably, in the step A), the pressure of the reaction furnace 3 is-0.5 to 0.5MPa.
Preferably, the carbon-containing gas is at least one of methane, ethane, ethylene, acetylene, carbon monoxide, carbon dioxide, ethanol, propylene, propane, butane, butadiene, pentane, pentene, benzene, and toluene.
Preferably, the doping gaseous source is a gaseous material source of doping elements; the doped solid source is a solid material source of doping elements;
wherein,
the doping element is at least one of nitrogen, boron, phosphorus, fluorine, sulfur, chlorine, bromine and iodine.
Preferably, the heating temperature of the heating system 2-1 is 100-800 ℃.
Preferably, the carrier gas is hydrogen or an inert gas.
The invention provides a device and a method for preparing doped graphene, wherein a carbon source, a doped gaseous source or a doped solid source and carrier gas are formed into bubbles through an aerator and are introduced into molten metal, and single-element or multi-element doped graphene is obtained by adjusting the type and concentration of the doped gas or the type and weight of the solid, so that a means for effectively preparing the doped graphene is provided for the prior art. The method can prepare the graphene doped in situ, does not need to add a catalyst, effectively simplifies the production process of the doped graphene, and can continuously prepare the graphene material doped with single element or co-doped with multiple elements by a one-step method. The doping source can be gas or solid, so that the doping range is enlarged, multiple elements can be doped simultaneously, the number of layers of the doped graphene is adjustable, and the doping elements and the doping concentration are easy to control. The method is simple and feasible, has high efficiency, uniform doping and high stability, and can be used for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of an apparatus for preparing doped graphene according to the present invention;
fig. 2 is a scanning electron microscope image of doped graphene obtained in embodiment 4 of the present invention;
FIG. 3 is a laser Raman spectrum of doped graphene obtained in example 4 of the present invention;
fig. 4 is an X-ray electron energy spectrum of the doped graphene obtained in example 4 of the present invention.
Detailed Description
The invention provides a device for preparing doped graphene, which comprises:
a gas mixing device 1;
a solid source bin 2 with an air inlet communicated with an air outlet of the air mixing device 1;
a reaction furnace 3 with a feed inlet communicated with a discharge outlet of the solid source bin 2; wherein, a flowmeter 4 and an aerator 5 are also arranged on the connecting pipeline between the solid source bin 2 and the reaction furnace 3;
the collecting device 6 is communicated with the discharge port of the reaction furnace 3;
a gas recovery device 7 with a gas inlet communicated with the gas outlet of the collection device 6;
wherein,
a heating system 2-1 and a material tray 2-2 are arranged in the solid source bin 2; the heating system 2-1 is also connected with a temperature control device 2-3.
Referring to fig. 1, fig. 1 is a schematic diagram of an apparatus for preparing doped graphene according to the present invention; wherein, 1 is a gas mixing device, 2 is a solid source bin, 2-1 is a heating system, 2-2 is a material tray, 2-3 is a temperature control device, 3 is a reaction furnace, 4 is a flow meter, 5 is an aerator, 6 is a collecting device, and 7 is a gas recovery device.
And 1 is a gas mixing device for receiving the carbon-containing gas, the carrier gas and the doped gaseous source or the carbon-containing gas and the carrier gas and mixing the received gases to form the gas mixture.
And 2 is a solid source bin, and an air inlet of the solid source bin is communicated with an air outlet of the air mixing device 1. In the invention, a heating system 2-1 and a material tray 2-2 are arranged in a solid source bin 2; wherein, heating system 2-1 is connected with charging tray 2-2, can heat charging tray 2-2. Specifically, the heating system 2-1 is fixedly connected to the bottom of the solid source bin 2, and the material tray 2-2 is connected to the heating system 2-1. In the invention, the heating system 2-1 is also connected with the temperature control device 2-3, and the temperature of the heating system 2-1 is controlled by the temperature control device 2-3.
And 3 is a reaction furnace, the feed inlet of which is communicated with the discharge outlet of the solid source bin 2 and is mainly used for receiving materials from the gas mixing device 1 or materials from the gas mixing device 1 and the solid source bin 2 and reacting in the reaction furnace to form doped graphene. In the invention, a flowmeter 4 and an aerator 5 are also arranged on a connecting pipeline between the solid source bin 2 and the reaction furnace 3. Specifically, the flow meter 4 is disposed at one end near the solid source bin 2, and the aerator 5 is disposed at one end near the reaction furnace 3. More specifically, the aerator 5 is disposed in the bottom portion immediately adjacent to the reaction furnace 3 for aerating the mixed gas to form bubbles directly entering from the bottom portion of the reaction furnace 3.
6 is a collecting device, and the feed inlet of the collecting device is communicated with the discharge outlet of the reaction furnace 3; specifically, the feed inlet of the collecting device 6 is communicated with the top discharge port of the reaction furnace 3, and products (doped graphene and hydrogen) generated after the reaction in the reaction furnace 3 are discharged from the top and enter the collecting device 6. In one embodiment of the present invention, a graphene filter is disposed in the collecting device 6; specifically, after the doped graphene enters the collecting device 6 along with hydrogen, the graphene products are collected through the graphene filter, and the rest gas continues to enter the next link.
And 7 is a gas recovery device, and the gas inlet of the gas recovery device is communicated with the gas outlet of the collecting device 6. After the doped graphene is collected by the collecting device 6, the remaining gas is continuously discharged and enters the gas recovery device 7 for recovery. Specifically, the surplus gas is compressed in the gas recovery device 7 and recovered.
The invention also provides a method for preparing the doped graphene, which is prepared by using the device for preparing the doped graphene in the technical scheme; the preparation process comprises the following steps:
a) Placing a metal catalyst in a reaction furnace 3, and performing gas replacement on the reaction furnace 3 to form an inert atmosphere in the reaction furnace; then heating the reaction furnace 3 to melt the metal catalyst to form molten metal;
b) Carrying out step b 1), b 2) or b 3):
b1 Introducing a carbon-containing gas, a carrier gas and a doping gaseous source into a gas mixing device 1 to be mixed to form a mixed gas, controlling the flow of the mixed gas through a flowmeter 4, introducing the mixed gas into a reaction furnace 3 from the bottom of the reaction furnace 3 to contact with molten metal in the reaction furnace 3 after aeration treatment by an aerator 5, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene;
or (b)
b2 Introducing carbon-containing gas and carrier gas into a gas mixing device 1 to be mixed to form mixed gas, opening a heating system 2-1 in a solid source bin 2 to heat a doped solid source in a charging tray 2-2, controlling the flow of the mixed gas through the heated solid source by a flowmeter 4, introducing the mixed gas into a reaction furnace 3 from the bottom of the reaction furnace 3 to be contacted with molten metal in the reaction furnace 3 after aeration treatment by an aerator 5, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene;
or (b)
b3 Introducing carbon-containing gas, carrier gas and doping gaseous source into a gas mixing device 1 to be mixed to form mixed gas, opening a heating system 2-1 in a solid source bin 2 to heat the doping solid source in a material tray 2-2, controlling the flow of the mixed gas through the heated solid source by a flowmeter 4, introducing the mixed gas into a reaction furnace 3 from the bottom of the reaction furnace 3 to be contacted with molten metal in the reaction furnace 3 after aeration treatment by an aerator 5, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene;
c) The doped graphene enters a collecting device 6 along with hydrogen, and the doped graphene is collected in the collecting device 6 to obtain a doped graphene product; the hydrogen gas continuously enters a gas recovery device (7) for recovery.
[ regarding step A ]:
a) Placing a metal catalyst in a reaction furnace 3, and performing gas replacement on the reaction furnace 3 to form an inert atmosphere in the reaction furnace; then, the reaction furnace 3 is heated to melt the metal catalyst to form a molten metal.
In the present invention, the metal catalyst is preferably at least one of iron, cobalt, nickel, copper, chromium, gold, silver, platinum, zinc, aluminum, chromium, manganese, titanium, tin, magnesium, gallium, indium, and palladium.
In the present invention, after the metal catalyst is placed in the reaction furnace 3, the reaction furnace 3 is subjected to gas substitution to form an inert atmosphere therein. Specifically, the reaction furnace 3 is vacuumized and then inert gas is introduced into the reaction furnace 3 for gas replacement, or the inert gas is directly introduced into the reaction furnace 3 for gas replacement; can be replaced a plurality of times, thereby forming an inert atmosphere in the reaction furnace 3. The kind of the inert gas is not particularly limited in the present invention, and may be a conventional protective gas in the art, such as nitrogen, helium or argon. In the present invention, the gas substitution is preferably performed by using an inert gas in the carrier gas (the carrier gas may be an inert gas as described later).
In the present invention, after the reaction furnace 3 is replaced with a gas to form an inert atmosphere therein, the reaction furnace 3 is heated to melt the metal catalyst to form a molten metal. In the present invention, the heating temperature is preferably 900 to 1700 ℃, and specifically 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃, 1700 ℃. The air pressure in the reaction furnace 3 is preferably-0.5 to 0.5MPa, and specifically-0.5 MPa, -0.3MPa, -0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, and 0.5MPa.
[ regarding step B ]:
in the present invention, step B) may be achieved in three ways, specifically by steps B1), B2) or B3). Wherein, step b 1) adopts a doping gaseous source, step b 2) adopts a doping solid source, and step b 3) adopts both the doping gaseous source and the doping solid source.
In the invention, the doping gaseous source is a gaseous substance source of doping elements; the doped solid source is a solid material source of a doping element. In the present invention, a doping gaseous source and a doping solid source are collectively referred to as a doping source. Wherein the doping element is preferably at least one of nitrogen, boron, phosphorus, fluorine, sulfur, chlorine, bromine and iodine. The doping source is a simple substance or a compound of doping elements. In the invention, when the doping element is nitrogen, the doping source is ammonia gas, phenol cyanine, amine organic matters, hydroxylamine organic matters, nitrile organic matters, diazo compounds or azo compounds. When the doping element is boron, the doping source is borane or an organic boride. When the doping element is phosphorus, the doping source is phosphide. When the doping element is sulfur, the doping source is sulfur powder, thiophene, thianthrene or thiourea and the like. When the doping element is fluorine, the doping source is fluorine gas, fluoromethane, fluoroethane, fluoroethylene, potassium fluoride or lithium fluoride, etc. When the doping element is chlorine, the doping source is chlorine, chloromethane, chloroethane or chloroethylene, etc. When the doping element is bromine, the doping source is bromine gas, methyl bromide or vinyl bromide and the like. When the doping element is iodine, the doping source is iodine gas, methyl iodide, ethyl iodide or vinyl iodide, etc.
Regarding step b 1):
b1 Introducing carbon-containing gas, carrier gas and doping gaseous source into the gas mixing device 1 to be mixed to form mixed gas, controlling the flow of the mixed gas through the flowmeter 4, introducing the mixed gas into the reaction furnace 3 from the bottom of the reaction furnace 3 to contact with molten metal in the reaction furnace 3 after aeration treatment through the aerator 5, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene.
In the present invention, the carbon-containing gas is preferably at least one of methane, ethane, ethylene, acetylene, carbon monoxide, carbon dioxide, ethanol, propylene, propane, butane, butadiene, pentane, pentene, benzene, and toluene.
In the present invention, the carrier is preferably hydrogen or an inert gas. The inert gas is not particularly limited in kind, and may be any inert gas conventionally used in the art, such as nitrogen, helium, or argon.
In the invention, when the carbon-containing gas, the carrier gas and the doping gas source are introduced into the gas mixing device 1, the volume of the doping gas source is preferably controlled to be 0.1% -5% of the total gas volume, and specifically can be 0.1%, 0.5%, 1%, 2%, 3%, 4% and 5%; the volume of the carbon-containing gas is preferably controlled to be 1% to 10% of the total gas volume, and may be specifically 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
In the invention, carbon-containing gas, carrier gas and doped gaseous source are introduced into a gas mixing device 1 to be mixed to form mixed gas, the flow rate of the mixed gas is controlled by a flowmeter 4, and the mixed gas enters a reaction furnace 3 and a reaction furnace from the bottom of the reaction furnace 3 after being aerated by an aerator 53. After the mixed gas is discharged from the gas mixing device 1, the mixed gas flows through the solid source bin 2 (the heating system does not need to be heated at the moment) and then flows through the flowmeter 4 to control the flow. Wherein the flow of the mixed gas is preferably controlled to be 5-15 m 3 And/h is 5m 3 /h、8m 3 /h、10m 3 /h、12m 3 /h、15m 3 And/h. The flow rate of the doped gas source in the mixed gas is preferably 0.1% -5% of the total gas flow rate (namely the flow rate is the same as the volume ratio in the previous step), and can be specifically 0.1%, 0.5%, 1%, 2%, 3%, 4% and 5%; the carbon-containing gas flow is preferably 1% -10% of the total gas flow (i.e. the flow ratio is the same as the previous volume ratio), and may be specifically 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%. In the invention, the mixed gas with the flow rate controlled by the flowmeter 4 enters the aerator 5 to be aerated to form bubbles, and enters the reaction furnace 3 from the bottom of the reaction furnace 3 to be contacted with the pre-melted metal in the reaction furnace 3.
In the invention, after the aerated gas is contacted with the molten metal in the reaction furnace 3, the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements under the condition of the existence of a doping gaseous source to form doped graphene. According to the invention, single-element or multi-element doped graphene can be obtained by adjusting the type and concentration of the doped gaseous source.
Regarding step b 2):
b2 Introducing carbon-containing gas and carrier gas into the gas mixing device 1 to be mixed to form mixed gas, opening a heating system 2-1 in the solid source bin 2 to heat the doped solid source in the charging tray 2-2, controlling the flow rate of the mixed gas through the heated solid source by a flowmeter 4, introducing the mixed gas into the reaction furnace 3 from the bottom of the reaction furnace 3 to be contacted with molten metal in the reaction furnace 3 after aeration treatment by an aerator 5, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene.
In the present invention, the carbon-containing gas is preferably at least one of methane, ethane, ethylene, acetylene, carbon monoxide, carbon dioxide, ethanol, propylene, propane, butane, butadiene, pentane, pentene, benzene, and toluene.
In the present invention, the carrier is preferably hydrogen or an inert gas. The inert gas is not particularly limited in kind, and may be any inert gas conventionally used in the art, such as nitrogen, helium, or argon.
In the present invention, when introducing the carbon-containing gas and the carrier gas into the gas mixing apparatus 1, the volume of the carbon-containing gas is preferably controlled to be 1% to 10% of the total gas volume, and specifically may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
In the invention, carbon-containing gas and carrier gas are introduced into a gas mixing device 1 to be mixed to form mixed gas, a heating system 2-1 in a solid source bin 2 is turned on to heat doped solid sources in a material tray 2-2 to form gas phases by the doped solid sources, and the mixed gas carries the doped sources converted into the gas phases by the heated solid sources, and the flow rate is controlled by a flowmeter 4. Wherein the mass ratio of the doped solid source to the introduced carbon-containing gas is preferably 1g to (0.05-1.0) L. The heating temperature for heating 2-1 is preferably 100 to 800 ℃, specifically 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃. After that, the gas enters the aerator 5 to be aerated to form bubbles and enters the reaction furnace 3 from the bottom of the reaction furnace 3 to be brought into contact with the metal in the reaction furnace 3 which has been melted in advance.
In the invention, after the aerated gas is contacted with the molten metal in the reaction furnace 3, the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements under the condition of the existence of doping sources to form doped graphene.
Regarding step b 3):
b3 Introducing carbon-containing gas, carrier gas and doping gaseous source into the gas mixing device 1 to mix to form mixed gas, opening a heating system 2-1 in the solid source bin 2 to heat the doping solid source in the material tray 2-2, controlling flow of the mixed gas through the heated solid source through a flowmeter 4, introducing the mixed gas into the reaction furnace 3 from the bottom of the reaction furnace 3 to contact with molten metal in the reaction furnace 3 after aeration treatment through an aerator 5, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene.
In the present invention, the carbon-containing gas is preferably at least one of methane, ethane, ethylene, acetylene, carbon monoxide, carbon dioxide, ethanol, propylene, propane, butane, butadiene, pentane, pentene, benzene, and toluene.
In the present invention, the carrier is preferably hydrogen or an inert gas. The inert gas is not particularly limited in kind, and may be any inert gas conventionally used in the art, such as nitrogen, helium, or argon.
In the invention, when the carbon-containing gas, the carrier gas and the doping gas source are introduced into the gas mixing device 1, the volume of the doping gas source is preferably controlled to be 0.1% -5% of the total gas volume, and specifically can be 0.1%, 0.5%, 1%, 2%, 3%, 4% and 5%; the volume of the carbon-containing gas is preferably controlled to be 1% to 10% of the total gas volume, and may be specifically 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
In the invention, carbon-containing gas, carrier gas and doped gaseous source are introduced into a gas mixing device 1 to be mixed to form mixed gas, a heating system 2-1 in a solid source bin 2 is opened to heat the doped solid source in a material tray 2-2 to form a gas phase by the doped solid source, and the mixed gas takes the doped source converted into the gas phase through the heated solid source and controls the flow rate together through a flowmeter 4. Wherein the mass ratio of the doped solid source to the introduced carbon-containing gas is preferably 1g to (0.05-1.0) L. The heating temperature for heating 2-1 is preferably 100 to 800 ℃, specifically 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃. After that, the gas enters the aerator 5 to be aerated to form bubbles and enters the reaction furnace 3 from the bottom of the reaction furnace 3 to be brought into contact with the metal in the reaction furnace 3 which has been melted in advance.
In the invention, after the aerated gas is contacted with the molten metal in the reaction furnace 3, the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements under the condition of the existence of doping sources to form doped graphene.
[ about step C ]:
c) The doped graphene enters a collecting device 6 along with hydrogen, and the doped graphene is collected in the collecting device 6 to obtain a doped graphene product; the hydrogen gas continues to enter the gas recovery device 7 for recovery.
In the invention, after the treatment in the step B), doped graphene and hydrogen are formed in the reaction furnace 3, the doped graphene enters the collecting device 6 along with the hydrogen, and the doped graphene is collected in the collecting device 6, so that a doped graphene product is obtained. Specifically, the doped graphene is filtered and collected by a filter in the collecting device 6, and the doped graphene is obtained. After the doped graphene is collected in the collecting device 6, the residual gas (hydrogen) continues to enter the gas recycling device 7 for recycling. Specifically, the surplus gas is compressed in the gas recovery device 7 and recovered.
The invention provides a device and a method for preparing doped graphene, wherein a carbon source, a doped gaseous source or a doped solid source and carrier gas are formed into bubbles through an aerator and are introduced into molten metal, and single-element or multi-element doped graphene is obtained by adjusting the type and concentration of the doped gas or the type and weight of the solid, so that a means for effectively preparing the doped graphene is provided for the prior art. The method can prepare the graphene doped in situ, does not need to add a catalyst, effectively simplifies the production process of the doped graphene, and can continuously prepare the graphene material doped with single element or co-doped with multiple elements by a one-step method. The doping source can be gas or solid, so that the doping range is enlarged, multiple elements can be doped simultaneously, the number of layers of the doped graphene is adjustable, and the doping elements and the doping concentration are easy to control. The method is simple and feasible, has high efficiency, uniform doping and high stability, and can be used for large-scale production.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
Comparative example 1: preparation of graphene
A) Placing 10L of copper metal catalyst in a reaction furnace 3, and performing gas replacement on the reaction furnace 3 to form inert atmosphere in the reaction furnace; then, the mixture was heated to 1200 ℃ (the pressure of the reaction furnace 3 was 0.01 MPa) to melt the metal.
B) The inlet switch of the carbon-containing gas methane and carrier gas hydrogen is opened, and methane (0.5 m) is introduced into the gas mixing device 1 3 /h) and hydrogen (9.5 m) 3 And/h) uniformly mixing, wherein the heating system 2-1 does not need to heat at the moment, and the mixed gas adjusts the inlet air flow rate through the flowmeter 4 (controls the total inlet air flow rate to be 10 m) 3 And (h) introducing the carbon-containing gas accounting for 5% of the total gas flow rate into the reaction furnace 3 from the bottom of the reaction furnace 3 to contact with molten metal in the reaction furnace 3 after being subjected to aeration treatment by the aerator 5, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen.
C) The graphene enters a collecting device 6 along with hydrogen, and the graphene is filtered and collected in the collecting device 6 to obtain a graphene product; the hydrogen gas continues to enter the gas recovery device 7 for recovery after being compressed.
And (3) product testing:
raman spectrum analysis is carried out on the obtained graphene product, and the result shows that the Raman spectrum of the graphene has two main peaks, and the G peak is 1580cm -1 Nearby, the 2D peak is 2700cm -1 Nearby. And at 1350cm -1 The nearby D peak is considered as a disordered oscillation peak of the graphene, and the ratio of the D peak to the G peak represents the defect density, and the larger the ID/IG ratio is, the higher the defect density is. The graphene obtained in comparative example 1 has an ID/IG of 0.09, indicating fewer structural defects in the graphene.
Example 1: preparation of doped graphene by gaseous source
A) Placing 10L of copper metal catalyst in a reaction furnace 3, and performing gas replacement on the reaction furnace 3 to form inert atmosphere in the reaction furnace; then, the mixture was heated to 1300℃and the pressure in the reactor 3 was 0.02MPa, to thereby melt the metal.
B) Opening an air inlet switch containing carbon gas methane and carrier gas hydrogen, and simultaneously introducing ammonia gas doping gaseous sourceThe three are uniformly mixed in the gas mixing device 1, the heating system 2-1 does not need to be heated at the moment, the mixed gas adjusts the inlet air flow rate through the flowmeter 4 (the total inlet air flow rate is controlled to be 10 m) 3 And (3) introducing carbon-containing gas accounting for 5% of the total gas flow, ammonia accounting for 2% of the total gas flow into the reaction furnace 3 from the bottom of the reaction furnace 3 after aeration treatment by the aerator 5, and contacting with molten metal in the reaction furnace 3, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements under the condition that a doping gaseous source exists to form N-doped graphene.
C) The N-doped graphene enters a collecting device 6 along with hydrogen, and the graphene is filtered and collected in the collecting device 6 to obtain an N-doped graphene product; the hydrogen gas continues to enter the gas recovery device 7 for recovery after being compressed.
And (3) product testing:
and the obtained doped graphene is subjected to laser Raman spectrum detection, so that the ID/IG of the doped graphene is 0.23, compared with the pure graphene of comparative example 1, the ID/IG of the product of example 1 is obviously increased, the defect density is obviously increased, and the successful preparation of the doped product is reflected.
Example 2: preparation of doped graphene by gaseous source
A) 7L of copper and 3L of nickel metal catalyst are placed in a reaction furnace 3, and the reaction furnace 3 is subjected to gas replacement to form inert atmosphere inside; then, the mixture was heated to 1600℃and the pressure in the reactor 3 was 0.05MPa to melt the metal.
B) Opening an air inlet switch containing methane gas and carrier gas argon gas, simultaneously introducing ammonia gas and diborane doped gaseous source, uniformly mixing the mixture in the air mixing device 1, heating the heating system 2-1 at the moment without heating, and regulating the air inlet flow of the mixed air through the flowmeter 4 (controlling the total air inlet flow to be 10 m) 3 And/h, wherein the carbon-containing gas accounts for 5% of the total gas flow, the ammonia accounts for 1% of the total gas flow, the diborane accounts for 1% of the total gas flow, and then the mixture is aerated by an aerator 5 and enters the reaction furnace 3 from the bottom of the reaction furnace 3 to contact with molten metal in the reaction furnace 3, wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene and the hydrogen exist in a doped gaseous sourceUnder the condition of (1) the graphene is doped into the doping element to form the N-B doped graphene.
C) The N-B doped graphene enters a collecting device 6 along with hydrogen, and the graphene is filtered and collected in the collecting device 6 to obtain an N-B doped graphene product; the hydrogen gas continues to enter the gas recovery device 7 for recovery after being compressed.
And (3) product testing:
and carrying out laser Raman spectrum detection on the obtained doped graphene, wherein the ID/IG is 0.35.
Example 3: preparation of doped graphene from solid source
A) Placing 10L of copper metal catalyst in a reaction furnace 3, and performing gas replacement on the reaction furnace 3 to form inert atmosphere in the reaction furnace; then, the mixture was heated to 1400℃and the pressure in the reactor 3 was 0.04MPa to melt the metal.
B) Opening an air inlet switch containing carbon gas methane and carrier gas hydrogen, uniformly mixing the carbon gas methane and the carrier gas hydrogen in an air mixing device 1 to form mixed air, opening a heating system 2-1 to heat a doped solid source (the heating temperature is 120 ℃, and the doped solid source thianthrene 3g is placed in the material disc 2-2 in advance) in a material disc 2-2 so that the doped solid source forms a gas phase, taking the mixed air into the gas phase by the heated solid source, and controlling the flow rate (the total air inlet flow rate is 10 m) through a flowmeter 4 together with the mixed air 3 And/h, the carbon-containing gas accounts for 5% of the total gas flow). After that, the gas enters the aerator 5 to be aerated to form bubbles and enters the reaction furnace 3 from the bottom of the reaction furnace 3 to be brought into contact with the metal in the reaction furnace 3 which has been melted in advance. The carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped into doping elements under the condition that a doping source exists to form N-S doped graphene.
C) The N-S doped graphene enters a collecting device 6 along with hydrogen, and the graphene is filtered and collected in the collecting device 6 to obtain an N-S doped graphene product; the hydrogen gas continues to enter the gas recovery device 7 for recovery after being compressed.
And (3) product testing:
and carrying out laser Raman spectrum detection on the obtained doped graphene, wherein the ID/IG is 0.33.
Example 4: co-production of doped graphene from gaseous and solid sources
A) 7L of copper and 3L of nickel metal catalyst are placed in a reaction furnace 3, and the reaction furnace 3 is subjected to gas replacement to form inert atmosphere inside; then, the mixture was heated to 1550 ℃ (the pressure of the reaction furnace 3 was 0.1 MPa) to melt the metal.
B) Opening an air inlet switch containing carbon gas methane and carrier gas argon, simultaneously introducing an ammonia gas doping gaseous source, uniformly mixing the carbon gas methane and the carrier gas argon in the air mixing device 1 to form mixed air, opening a heating system 2-1 to heat a doping solid source in a material tray 2-2 (the heating temperature is 150 ℃, the doping solid source thianthrene 3g is placed in the material tray 2-2 in advance) so that the doping solid source forms a gas phase, taking the doping source converted into the gas phase by the mixed air through the heating solid source, and controlling the flow (the total air inlet flow is 10 m) through a flowmeter 4 together 3 And/h, the carbon-containing gas accounts for 4% of the total gas flow, and the ammonia accounts for 1% of the total gas flow). After that, the gas enters the aerator 5 to be aerated to form bubbles and enters the reaction furnace 3 from the bottom of the reaction furnace 3 to be brought into contact with the metal in the reaction furnace 3 which has been melted in advance. The carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped into doping elements under the condition that a doping source exists to form N-S doped graphene.
C) The N-S doped graphene enters a collecting device 6 along with hydrogen, and the graphene is filtered and collected in the collecting device 6 to obtain an N-S doped graphene product; the hydrogen gas continues to enter the gas recovery device 7 for recovery after being compressed.
And (3) product testing:
and carrying out scanning electron microscope characterization on the obtained doped graphene, wherein the result is shown in figure 2.
And carrying out laser Raman spectrum detection on the obtained doped graphene, wherein the result is shown in figure 3. The resulting product can be represented by figures 2-3 as a graphene product and has an ID/IG of 0.41. And carrying out multiple Raman tests on the obtained doped graphene, wherein the test results are basically consistent, and the doping uniformity of the doped graphene is proved.
And carrying out X-ray electron energy spectrum test on the obtained doped graphene, wherein the result is shown in fig. 4, and the result shows that N and S elements are doped in the graphene.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. An apparatus for preparing doped graphene, comprising:
a gas mixing device (1);
the air inlet is communicated with the air outlet of the air mixing device (1);
the feed inlet is communicated with the discharge outlet of the solid source bin (2); wherein, a flowmeter (4) and an aerator (5) are also arranged on the connecting pipeline between the solid source bin (2) and the reaction furnace (3);
the collecting device (6) is communicated with the discharge port of the reaction furnace (3) at the feed port;
the gas recovery device (7) is communicated with the gas outlet of the collecting device (6);
wherein,
a heating system (2-1) and a material tray (2-2) are arranged in the solid source bin (2); the heating system (2-1) is also connected with a temperature control device (2-3).
2. The device for preparing doped graphene according to claim 1, characterized in that a graphene filter is provided in the collecting device (6).
3. A method for preparing doped graphene, characterized in that the preparation is performed by using the apparatus for preparing doped graphene according to any one of claims 1 to 2; the preparation process comprises the following steps:
a) Placing a metal catalyst in a reaction furnace (3), and performing gas replacement on the reaction furnace (3) to form an inert atmosphere in the reaction furnace; then heating the reaction furnace (3) to melt the metal catalyst to form molten metal;
b) Carrying out step b 1), b 2) or b 3):
b1 Introducing carbon-containing gas, carrier gas and doping gaseous source into a gas mixing device (1) to be mixed to form mixed gas, controlling the flow of the mixed gas through a flowmeter (4), introducing the mixed gas into a reaction furnace (3) from the bottom of the reaction furnace (3) to be contacted with molten metal in the reaction furnace (3) after aeration treatment of an aerator (5), wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene;
or (b)
b2 Introducing carbon-containing gas and carrier gas into a gas mixing device (1) to be mixed to form mixed gas, opening a heating system (2-1) in a solid source bin (2) to heat a doped solid source in a material tray (2-2), controlling flow of the mixed gas through a flowmeter (4) by the heated solid source, introducing the mixed gas into the reaction furnace (3) from the bottom of the reaction furnace (3) to be in contact with molten metal in the reaction furnace (3) after aeration treatment through an aerator (5), wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene;
or (b)
b3 Introducing carbon-containing gas, carrier gas and doping gaseous source into a gas mixing device (1) to be mixed to form mixed gas, opening a heating system (2-1) in a solid source bin (2) to heat doping solid source in a material tray (2-2), controlling flow of the mixed gas through a flow meter (4) by the heated solid source, introducing the mixed gas into the reaction furnace (3) from the bottom of the reaction furnace (3) to be in contact with molten metal in the reaction furnace (3) after aeration treatment through an aerator (5), wherein the carbon-containing gas is cracked under the catalysis of the molten metal to generate graphene and hydrogen, and the graphene is doped with doping elements to form doped graphene;
c) The doped graphene enters a collecting device (6) along with hydrogen, and the doped graphene is collected in the collecting device (6) to obtain a doped graphene product; the hydrogen gas continuously enters a gas recovery device (7) for recovery.
4. The method of claim 1, wherein the metal catalyst is at least one of iron, cobalt, nickel, copper, chromium, gold, silver, platinum, zinc, aluminum, chromium, manganese, titanium, tin, magnesium, gallium, indium, and palladium.
5. The method according to claim 1, wherein in step a), the heating is performed at a temperature of 900 to 1700 ℃.
6. The method according to claim 1, characterized in that in step a) the pressure of the reactor (3) is-0.5 to 0.5MPa.
7. The method of claim 1, wherein the carbon-containing gas is at least one of methane, ethane, ethylene, acetylene, carbon monoxide, carbon dioxide, ethanol, propylene, propane, butane, butadiene, pentane, pentene, benzene, and toluene.
8. The method of claim 1, wherein the dopant gaseous source is a gaseous source of dopant elements; the doped solid source is a solid material source of doping elements;
wherein,
the doping element is at least one of nitrogen, boron, phosphorus, fluorine, sulfur, chlorine, bromine and iodine.
9. The method according to claim 7, characterized in that the heating temperature of the heating system (2-1) is 100-800 ℃.
10. The method of claim 1, wherein the carrier gas is hydrogen or an inert gas.
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| CN101289181A (en) * | 2008-05-29 | 2008-10-22 | 中国科学院化学研究所 | Doped graphene and method for preparing same |
| CN106011779A (en) * | 2016-06-23 | 2016-10-12 | 电子科技大学 | Method for preparing sulfur-doped graphene thin films |
| CN106435632A (en) * | 2016-09-20 | 2017-02-22 | 南昌大学 | Preparation method for boron-doped graphene |
| CN113233447A (en) * | 2021-06-07 | 2021-08-10 | 湖北犇星新材料股份有限公司 | Method for continuously synthesizing doped graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289181A (en) * | 2008-05-29 | 2008-10-22 | 中国科学院化学研究所 | Doped graphene and method for preparing same |
| CN106011779A (en) * | 2016-06-23 | 2016-10-12 | 电子科技大学 | Method for preparing sulfur-doped graphene thin films |
| CN106435632A (en) * | 2016-09-20 | 2017-02-22 | 南昌大学 | Preparation method for boron-doped graphene |
| CN113233447A (en) * | 2021-06-07 | 2021-08-10 | 湖北犇星新材料股份有限公司 | Method for continuously synthesizing doped graphene |
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