CN109970046B - Preparation method of carbon nano tube with thin tube diameter - Google Patents
Preparation method of carbon nano tube with thin tube diameter Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/159—Carbon nanotubes single-walled
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/158—Carbon nanotubes
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- C01B32/162—Preparation characterised by catalysts
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/04—Nanotubes with a specific amount of walls
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- C01B2202/00—Structure or properties of carbon nanotubes
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
Abstract
The invention belongs to the technical field of new materials, and relates to a preparation method of a carbon nano tube with a thin tube diameter, which comprises the following steps: generating an iron-containing metal organic framework compound from iron ions and an organic ligand by a solvothermal method, infiltrating a solution containing rare earth ions after separation, washing and drying, and then carbonizing in inert gas to obtain an iron-loaded porous carbon material; then directly using the carbon source and the catalyst as a solid carbon source and a catalyst, spraying the carbon source and the catalyst from a plasma torch by adopting a high-temperature plasma method, gasifying the carbon source and the catalyst by high temperature, and then growing the carbon nano tube when descending and cooling. The porous carbon material derived from the metal organic framework compound can ensure that the original iron element obtains uniform distribution of ultrafine particles, and the porous carbon is favorable for high-temperature gasification, provides an ultrafine nano catalyst and a high-activity carbon source for the growth of the ultrafine carbon nano tube, greatly improves the growth efficiency of the carbon nano tube with the small diameter, is an effective means for preparing the carbon nano tube with the small diameter and the single-wall carbon nano tube, and has important practical application value.
Description
Technical Field
The invention belongs to the technical field of new materials, relates to a nano carbon material, and particularly relates to a preparation method of a carbon nano tube with a small tube diameter.
Background
The carbon nano tube is a one-dimensional tubular nano structure formed by carbon-carbon covalent bonds, has an intact crystalline carbon structure, shows attractive application prospects in the fields of mechanics, electricity, thermology and the like, and has wide application prospects in the fields of structural composite materials, conductive fillers, energy sources, heat management and functional devices. Particularly in the field of mechanical enhancement and conductive filling, the advantages of one-dimensional nano structure and self characteristics are combined, so that the composite material is expected to become a bulk base material and has huge potential market scale compared with the traditional filling modified material.
The carbon nano tube can be divided into a single-walled carbon nano tube and a multi-walled carbon nano tube according to the structure, the lower the conductive threshold value when the carbon nano tube is used for conductive filler along with the thinning of the tube diameter, particularly the conductive threshold value of the single-walled carbon nano tube with the tube diameter lower than 2 nanometers can be as low as one ten thousandth, and the carbon nano tube cannot be obtained by the conventional material. Therefore, the development of the carbon nanotubes with small tube diameter and even the single-walled carbon nanotubes is a key main flow direction for practically promoting the application of the carbon nanotubes in the field of conductive fillers. At present, the preparation method of the carbon nanotube mainly comprises the following steps: chemical vapor deposition, arc ablation, laser, plasma, etc., wherein chemical vapor deposition is a relatively mature process route, has been industrially applied. However, the chemical vapor deposition method has the defects of low degree of crystallization of the carbon nanotubes due to the inherent low reaction temperature, so that the defect content of the carbon nanotubes prepared by the chemical vapor deposition method is high, and the electrical conductivity of the carbon nanotubes prepared by the chemical vapor deposition method is far from being compared with high-temperature preparation methods such as a laser method, an arc method, a plasma method and the like. Because the surface curvature radius of the carbon nano tube with the thin tube diameter is small, the carbon-carbon distortion is serious, and the bonding potential barrier is very high. Because the reaction temperature of the traditional chemical vapor deposition method is low, the carbon-carbon can not well cross the bonding potential barrier in the reconstruction process, a large number of incomplete sp2 structures are often formed, the internal defects of the carbon nano tube are caused, the electron transmission is seriously hindered, and the electrical conductivity of the carbon nano tube is reduced. Therefore, improving the catalyst activity or raising the reaction temperature is a key element for preparing the carbon nano tube with the small tube diameter. However, most high temperature reaction routes are transient high temperature, and how to keep the fine size of the carbon nanotube growth catalyst is the most core technology for controlling the tube diameter of the carbon nanotube. Because most of the methods for preparing the carbon nano tube at high temperature can reach 2000 ℃ or even 20000 ℃ in a high-temperature area, most of metal particles used as the catalyst are already in a liquid state, are easy to fuse and grow up, and even lose the activity of the metal particles. Therefore, it is an important difficulty in the field of high-crystallinity and fine-diameter carbon nanotube preparation to obtain a high-temperature reaction environment and to avoid catalytic growth and even inactivation.
The Chinese patent 201010234322.4 discloses a method for preparing single-walled carbon nanotubes with controllable diameters, which adopts a high-temperature arc ablation method to fill carbon powder and metal catalysts into carbon electrodes, and prepares the carbon nanotubes by direct arc ablation. The chinese patent 200610040936.2 discloses a method for preparing carbon nanotubes by using a high-power plasma generator, which directly injects coal powder into high-temperature plasma to prepare multi-walled carbon nanotubes with large tube diameters mostly. Since the high-temperature processes cannot accurately control the uniform distribution of the catalyst at high temperature, the effective control of the tube diameter of the carbon nanotube is still a challenging task. Chinese patent 201110315452.5 discloses a method for preparing carbon nanotubes, which comprises loading a metal salt solution on a molybdenum or zirconium substrate, placing on a deposition table in a chamber of a dc plasma jet chemical vapor deposition apparatus, forming a high temperature plasma by a dc arc, decomposing and reducing the metal salt to form a Ni/MgO catalyst, and introducing a hydrocarbon gas to crack at high temperature to form carbon nanotubes. The high-temperature growth process can artificially control the structure of the catalyst, but is only suitable for growth with a substrate, and the catalyst is easy to fuse and agglomerate at high temperature, so that the controllable preparation of the carbon nano tube with high crystallinity and small tube diameter still has great difficulty.
Disclosure of Invention
The main objective of the present invention is to provide a method for preparing carbon nanotubes with small tube diameter, so as to solve any one of the above and other potential problems in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps: a method for preparing carbon nanotubes with thin tube diameters specifically comprises the following steps:
s1, preparing a metal organic framework compound containing iron;
s2, separating, washing and drying the iron-containing metal organic framework compound prepared in the step S1, soaking the iron-containing metal organic framework compound in a solution containing rare earth ions, and then carbonizing the iron-containing metal organic framework compound in inert gas to obtain a porous carbon material loaded with iron and rare earth elements;
and S3, treating the porous carbon material loaded with iron and rare earth elements by using a high-temperature plasma torch, gasifying a carbon source and a catalyst by using high temperature, and obtaining the carbon nano tube with the tube diameter less than or equal to 5 nanometers in a descending process.
According to an embodiment of the present disclosure, the carbon nanotube is a multi-walled carbon nanotube, a double-walled carbon nanotube, or a single-walled carbon nanotube.
According to an embodiment of the disclosure, the preparation method of the iron-containing metal organic framework compound in S1 comprises the following steps:
s1.1, uniformly mixing iron salt containing iron ions, an organic ligand and a solvent; the molar ratio of iron ions in the iron salt containing iron ions to organic ligands is 1: 0.5-1: 4;
s1.2, carrying out solvothermal reaction on the uniformly mixed reaction system of S1.1 at 100-300 ℃ for 2-72 hours, cooling the reaction liquid to room temperature, filtering and separating, washing the obtained solid, and carrying out vacuum drying at 40-100 ℃ for 2-12 hours to obtain the iron-containing metal organic framework compound.
According to the embodiment of the disclosure, the iron salt containing iron ions in S1 is any one or a combination of two or more of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate;
the organic ligand comprises an aromatic carboxylic acid ligand, and the aromatic carboxylic acid ligand comprises any one or the combination of more than two of phthalic acid, terephthalic acid, trimesic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid and biphenyl tetracarboxylic acid;
the solvent is any one of NN-dimethylformamide and NN-diethylformamide.
According to the embodiment of the disclosure, the concentration of the rare earth ion solution in the S2 is 0.001-0.1 mol/L, and the rare earth ion solution is soluble yttrium salt or soluble lanthanum salt; the soluble yttrium salt comprises yttrium nitrate, yttrium oxalate and yttrium chloride; the soluble lanthanum salts include lanthanum nitrate, lanthanum oxalate, lanthanum chloride, cerium nitrate, cerium oxalate and cerium chloride.
According to the embodiment of the disclosure, the inert gas in the carbonization step in S2 is any one or a combination of nitrogen and argon, the carbonization temperature is 400 ℃ and 700 ℃, and the carbonization time is 10 minutes to 2 hours.
According to the embodiment of the disclosure, the specific process of S3 is as follows: firstly, vacuumizing a plasma reaction cavity to 200-800Torr, then introducing arc-starting gas into a plasma spray gun to obtain a stable high-temperature plasma torch, then injecting a porous carbon material loaded with iron and rare earth into the plasma reaction cavity through carrier gas (and/or supplementing an organic carbon source from the side surface of the plasma torch), and entering the ion reaction cavity through the center of the plasma torch, so that the carbon nano tube product with the thin tube diameter can be collected on the inner wall and the bottom of the reaction cavity. The organic carbon source is any one of methane, ethylene, ethanol and methanol.
According to the disclosed embodiment, the power of the high temperature plasma torch in the S3 is >10kW, the maximum flame temperature is >2000 ℃; the high temperature plasma torch includes radio frequency plasma, arc plasma, and microwave plasma.
According to the embodiment of the disclosure, the arc striking gas is mixed gas of argon and helium =1: 10-10: 1; the carrier gas is argon gas and hydrogen gas =100: 1-10.
According to the embodiment of the disclosure, the injection flow rate of the porous carbon material loaded with iron and rare earth is 0.1-10 g/s, and the injection mode is intermittent or continuous according to the volume of the plasma reaction cavity and the product collection mode.
Compared with the prior art, the invention has the advantages that:
(1) the organic metal framework compounds (MOFs) are used as the catalyst and the solid carbon source, the characteristic of uniform structure of the MOFs is fully utilized, the iron particles of the catalyst can be uniformly distributed in the carbon material matrix through the carbonization process, the uniform dispersion of atomic scale can be achieved, the fusion growth of the catalyst particles at high temperature can be avoided, and the uncontrollable pipe diameter structure caused by the subsequent catalytic growth of the carbon nano tube due to the nonuniform size of the catalyst is avoided;
(2) the catalyst iron particles are in a superfine nano-scale state, and the porous carbon material has huge surface area and activity, so that the catalyst iron particles can be rapidly gasified after passing through a high-temperature plasma torch, the impurities of the non-carbon nano-tube are obviously reduced, and the purity is improved;
(3) the MOFs material is adopted to soak rare earth ions, and oxides of rare earth yttrium, cerium, lanthanum and the like formed subsequently are uniformly dispersed in the porous carbon material, so that the carbon dissolving capacity of the catalyst iron can be regulated and controlled, the growth of a crystallized carbon nanotube is facilitated, and the utilization rate of the rare earth ions is also improved;
(4) the high-temperature plasma process can obtain the ultra-high growth temperature of the carbon nano tube, and has obvious advantages for crossing the growth potential barrier of the small-caliber carbon nano tube and improving the crystallinity.
Drawings
FIG. 1 is a process flow chart of a method for preparing carbon nanotubes with small tube diameter according to the present invention.
Detailed Description
The technical solution of the present invention is further explained with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, the method for preparing a carbon nanotube with a small diameter of the present invention specifically comprises:
s1, preparing a metal organic framework compound containing iron;
s2, separating, washing and drying the iron-containing metal organic framework compound prepared in the step S1, soaking the iron-containing metal organic framework compound in a solution containing rare earth ions, and then carbonizing the iron-containing metal organic framework compound in inert gas to obtain a porous carbon material loaded with iron and rare earth elements;
and S3, treating the porous carbon material loaded with iron and rare earth elements by using a high-temperature plasma torch to obtain the carbon nano tube with the tube diameter less than or equal to 5 nanometers in a descending process.
According to an embodiment of the present disclosure, the carbon nanotube is a multi-walled carbon nanotube, a double-walled carbon nanotube, or a single-walled carbon nanotube.
According to an embodiment of the disclosure, the preparation method of the iron-containing metal organic framework compound in S1 comprises the following steps:
s1.1, uniformly mixing iron salt containing iron ions, an organic ligand and a solvent; the molar ratio of iron ions in the iron salt containing iron ions to organic ligands is 1: 0.5-1: 4;
s1.2, carrying out solvothermal reaction on the uniformly mixed reaction system of S1.1 at 100-300 ℃ for 2-72 hours, cooling the reaction liquid to room temperature, filtering and separating, washing the obtained solid, and carrying out vacuum drying at 40-100 ℃ for 2-12 hours to obtain the iron-containing metal organic framework compound.
According to the embodiment of the disclosure, the iron salt containing iron ions in S1 is any one or a combination of two or more of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate;
the organic ligand comprises an aromatic carboxylic acid ligand, and the aromatic carboxylic acid ligand comprises any one or the combination of more than two of phthalic acid, terephthalic acid, trimesic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid and biphenyl tetracarboxylic acid;
the solvent is any one of NN-dimethylformamide and NN-diethylformamide.
According to the embodiment of the disclosure, the concentration of the rare earth ion solution in the S2 is 0.001-0.1 mol/L, and the rare earth ion solution is soluble yttrium salt or soluble lanthanum salt; the soluble yttrium salt comprises yttrium nitrate, yttrium oxalate and yttrium chloride; the soluble lanthanum salts include lanthanum nitrate, lanthanum oxalate, lanthanum chloride, cerium nitrate, cerium oxalate and cerium chloride.
According to the embodiment of the disclosure, the inert gas in the carbonization step in S2 is any one or a combination of nitrogen and argon, the carbonization temperature is 400 ℃ and 700 ℃, and the carbonization time is 10 minutes to 2 hours.
According to the embodiment of the disclosure, the specific process of S3 is as follows: firstly, vacuumizing a plasma reaction cavity to 200-800Torr, then introducing arc-starting gas into a plasma spray gun to obtain a stable high-temperature plasma torch, then injecting a porous carbon material loaded with iron and rare earth into the ion reaction cavity through the center of the plasma torch by carrier gas, and collecting the carbon nano tube product with the small tube diameter on the inner wall and the bottom of the reaction cavity.
According to the disclosed embodiment, the power of the high temperature plasma torch in the S3 is >10kW, the maximum flame temperature is >2000 ℃; the high temperature plasma torch includes radio frequency plasma, arc plasma, and microwave plasma.
According to the embodiment of the disclosure, the arc striking gas is mixed gas of argon and helium =1: 10-10: 1; the carrier gas is argon gas and hydrogen gas =100: 1-10; or supplementing organic carbon source from the side surface of the plasma gun, and descending along with the plasma gun into any one of methane, ethylene, ethanol, methanol and the like.
According to the embodiment of the disclosure, the injection flow rate of the porous carbon material loaded with iron and rare earth is 0.1-10 g/s, and the injection mode is intermittent or continuous according to the volume of the plasma reaction cavity and the product collection mode.
Example 1
Carrying out solvothermal reaction on 0.01 mol/L ferric chloride and 0.02 mol/L terephthalic acid in NN-dimethylformamide at 150 ℃ for 24 hours, separating, washing, and drying in vacuum at 60 ℃ to obtain the metal organic framework compound containing iron ions. And then soaking the porous carbon material in 0.01 mol/L yttrium nitrate solution, separating and drying the porous carbon material, and carbonizing the porous carbon material at 500 ℃ for 2 hours in a nitrogen atmosphere to obtain the porous carbon material loaded with iron and rare earth. A50 Kw radio frequency plasma spraying device is used as a high-temperature heat source, a plasma cavity is firstly vacuumized to 500Torr, then argon gas, namely helium gas =1:5 mixed arc striking gas, is introduced into a plasma spray gun, a power supply of the device is started to obtain a stable plasma torch, then a porous carbon material loaded with iron and rare earth is injected by mixed carrier gas, namely argon gas, namely hydrogen gas =95:5, with the injection flow of 0.5 g/s, enters an ion reaction cavity through the center of the plasma torch, and after the reaction is carried out for 20 minutes, a carbon nano tube product with a small tube diameter can be collected on the inner wall and the bottom of the reaction cavity. Collecting the product, observing the appearance of the product through a field emission scanning electron microscope, counting the pipe diameter distribution of the product, and finding that the pipe diameter is mainly 1-2 nanometers; the degree of crystallization of the product was qualitatively analyzed by the intensity ratio of the G and D peaks of the Raman spectrum, IG/ID=20。
Example 2
Carrying out solvothermal reaction on 1 mol/L ferric sulfate and 4 mol/L phthalic acid in NN-dimethylformamide at 200 ℃ for 72 hours, separating, washing, and drying in vacuum at 60 ℃ to obtain the metal organic framework compound containing iron ions. And then soaking the porous carbon material in 0.1 mol/L lanthanum nitrate solution, separating and drying the solution, and carbonizing the solution for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain the porous carbon material loaded with iron and rare earth. High-temperature heat source of 50Kw radio frequency plasma spraying equipmentFirstly, vacuumizing a plasma cavity to 500Torr, introducing mixed arc-starting gas of helium =1:2 into a plasma spray gun, starting a power supply of the equipment to obtain a stable plasma torch, then injecting the porous carbon material loaded with iron and rare earth into the ion reaction cavity through mixed carrier gas of argon =95:5, wherein the injection flow is 5 g/s, the porous carbon material enters the ion reaction cavity through the center of the plasma torch, simultaneously introducing ethylene from the side surface of the plasma torch to serve as a gas carbon source, and collecting the product of the carbon nano tube with the small tube diameter on the inner wall and the bottom of the reaction cavity after reacting for 20 minutes. Collecting the product, observing the appearance of the product through a field emission scanning electron microscope, counting the pipe diameter distribution of the product, and finding that the pipe diameter is mainly 3-5 nanometers; the degree of crystallization of the product was qualitatively analyzed by the intensity ratio of the G and D peaks of the Raman spectrum, IG/ID=1。
Example 3
Carrying out solvothermal reaction on 0.001 mol/L ferric nitrate and 0.002 mol/L trimesic acid in NN-dimethylformamide at 300 ℃ for 72 hours, separating, washing, and carrying out vacuum drying at 60 ℃ to obtain the metal organic framework compound containing iron ions. And then soaking the porous carbon material in a 0.001 mol/L cerium nitrate solution, separating and drying the solution, and carbonizing the solution for 2 hours at 500 ℃ in an argon atmosphere to obtain the porous carbon material loaded with iron and rare earth. A50 Kw radio frequency plasma spraying device is used as a high-temperature heat source, a plasma cavity is firstly vacuumized to 500Torr, then argon gas, namely helium gas =1:5 mixed arc starting gas, is introduced into a plasma spray gun, a power supply of the device is started to obtain a stable plasma torch, then a porous carbon material loaded with iron and rare earth is injected by argon gas, namely hydrogen gas =95:5 mixed carrier gas, the injection flow is 0.01 g/s, the porous carbon material enters an ion reaction cavity through the center of the plasma torch, simultaneously ethanol is introduced from the side face of the plasma torch to serve as a gas carbon source, and after the reaction is carried out for 20 minutes, the thin-pipe-diameter carbon nanotube product can be collected on the inner wall and the bottom of the reaction cavity. Collecting the product, observing the appearance of the product through a field emission scanning electron microscope, counting the pipe diameter distribution of the product, and finding that the pipe diameter is mainly 1-2 nanometers; the degree of crystallization of the product was qualitatively analyzed by the intensity ratio of the G and D peaks of the Raman spectrum, IG/ID=40。
Example 4
0.01 molCarrying out solvothermal reaction on iron acetate and 0.04 mol/L biphenyldicarboxylic acid in NN-dimethylformamide at 100 ℃ for 2 hours, separating, washing, and drying in vacuum at 60 ℃ to obtain the metal organic framework compound containing iron ions. And then soaking the porous carbon material in 0.01 mol/L yttrium nitrate solution, separating and drying the porous carbon material, and carbonizing the porous carbon material at 500 ℃ for 2 hours in a nitrogen atmosphere to obtain the porous carbon material loaded with iron and rare earth. A50 Kw radio frequency plasma spraying device is used as a high-temperature heat source, a plasma cavity is vacuumized to 500Torr, then argon gas, namely helium gas =1:5 mixed arc starting gas, is introduced into a plasma spray gun, a power supply of the device is turned on to obtain a stable plasma torch, then a porous carbon material loaded with iron and rare earth is injected by argon gas, namely hydrogen gas =95:5 mixed carrier gas, the injection flow is 0.5 g/s, the porous carbon material enters an ion reaction cavity through the center of the plasma torch, simultaneously methane is introduced from the side face of the plasma torch to serve as a gas carbon source, and after the reaction is carried out for 20 minutes, the products of the carbon nano tube with the small diameter can be collected on the inner wall and the bottom of the reaction cavity. Collecting the product, observing the appearance of the product through a field emission scanning electron microscope, counting the pipe diameter distribution of the product, and finding that the pipe diameter is mainly 3-5 nanometers; the degree of crystallization of the product was qualitatively analyzed by the intensity ratio of the G and D peaks of the Raman spectrum, IG/ID=2。
Example 5
Carrying out solvothermal reaction on 0.01 mol/L ferric chloride and 0.02 mol/L terephthalic acid in NN-diethylformamide at 200 ℃ for 36 hours, separating, washing, and drying in vacuum at 60 ℃ to obtain the metal organic framework compound containing iron ions. And then soaking the porous carbon material in 0.01 mol/L yttrium nitrate solution, separating and drying the porous carbon material, and carbonizing the porous carbon material for 30 minutes at 400 ℃ in an argon atmosphere to obtain the porous carbon material loaded with iron and rare earth. Taking 50kW radio frequency plasma spraying equipment as a high-temperature heat source, vacuumizing a plasma cavity to 500Torr, introducing mixed arc-starting gas of helium =1:5 into a plasma spray gun, starting an equipment power supply to obtain a stable plasma torch, injecting a porous carbon material loaded with iron and rare earth into the plasma reaction cavity through mixed carrier gas of argon, hydrogen =95:5 at an injection flow of 0.5 g/s, introducing methanol from the side face of the plasma torch to serve as a gas carbon source, and reacting 2And collecting the product of the carbon nano tube with the small diameter on the inner wall and the bottom of the reaction cavity after 0 minute. Collecting the product, observing the appearance of the product through a field emission scanning electron microscope, counting the pipe diameter distribution of the product, and finding that the pipe diameter is mainly 1-2 nanometers; the degree of crystallization of the product was qualitatively analyzed by the intensity ratio of the G and D peaks of the Raman spectrum, IG/ID=10。
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose the technical solution of the present invention, and further explain the technical solution, the implementation process and the principle thereof, etc.
Claims (10)
1. A preparation method of carbon nanotubes with thin tube diameters is characterized by specifically comprising the following steps:
s1, preparing a metal organic framework compound containing iron;
s2, selecting the iron-containing metal organic framework compound prepared in the step S1, separating, washing and drying the iron-containing metal organic framework compound, soaking the iron-containing metal organic framework compound in a solution containing rare earth ions, and then carbonizing the iron-containing metal organic framework compound in inert gas to obtain a porous carbon material loaded with iron and rare earth elements;
and S3, treating the porous carbon material loaded with iron and rare earth elements by using a high-temperature plasma torch, gasifying a carbon source and a catalyst by using high temperature, and obtaining the carbon nano tube with the tube diameter less than or equal to 5 nanometers in a descending process.
2. The method of claim 1, wherein: the carbon nanotube is a multi-walled carbon nanotube, a double-walled carbon nanotube or a single-walled carbon nanotube.
3. The method of claim 1, wherein: the preparation method of the iron-containing metal organic framework compound in S1 comprises the following steps:
s1.1, uniformly mixing iron salt containing iron ions, an organic ligand and a solvent; the molar ratio of iron ions in the iron salt containing iron ions to organic ligands is 1: 0.5-1: 4;
s1.2, carrying out solvothermal reaction on the uniformly mixed reaction system of S1.1 at 100-300 ℃ for 2-72 hours, cooling the reaction liquid to room temperature, filtering and separating, washing the obtained solid, and carrying out vacuum drying at 40-100 ℃ for 2-12 hours to obtain the iron-containing metal organic framework compound.
4. The method according to claim 3, wherein in S1
The ferric salt containing ferric ions is any one or the combination of more than two of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate;
the organic ligand comprises an aromatic carboxylic acid ligand, and the aromatic carboxylic acid ligand comprises any one or the combination of more than two of phthalic acid, terephthalic acid, trimesic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid and biphenyl tetracarboxylic acid;
the solvent is any one of NN-dimethylformamide and NN-diethylformamide.
5. The method of claim 1, wherein: the concentration of the rare earth ion solution in the S2 is 0.001-0.1 mol/L, and the rare earth ion solution is soluble yttrium salt or soluble lanthanide salt; the soluble yttrium salt comprises: yttrium nitrate, yttrium oxalate and yttrium chloride; the soluble lanthanide salts include lanthanum nitrate, lanthanum oxalate, lanthanum chloride, cerium nitrate, cerium oxalate, and cerium chloride.
6. The preparation method as claimed in claim 1, wherein the inert gas in the carbonization step in S2 is any one or combination of nitrogen and argon, the carbonization temperature is 400-700 ℃, and the carbonization time is 10 minutes-2 hours.
7. The method of claim 1, wherein: the specific process of S3 is as follows: firstly, vacuumizing a plasma reaction cavity to 200-800Torr, then introducing arc-starting gas into a plasma spray gun to obtain a stable high-temperature plasma torch, then injecting carrier gas into a porous carbon material loaded with iron and rare earth elements obtained by carbonization, and allowing the porous carbon material to enter the ion reaction cavity through the center of the plasma torch to obtain a carbon nano tube product.
8. The method of claim 7, wherein: the power of the high-temperature plasma torch in the S3 is more than 10kW, and the highest temperature of the flame is more than 2000 ℃; the high temperature plasma torch includes radio frequency plasma, arc plasma, and microwave plasma.
9. The method of claim 7, wherein: the arc striking gas is mixed gas of argon and helium in a ratio of 1: 10-10: 1; the carrier gas is argon and hydrogen in a ratio of 100: 1-10.
10. The method of claim 7, wherein: the injection flow rate of the porous carbon material loaded with iron and rare earth is 0.1-10 g/s, and the injection mode is intermittent or continuous according to the volume of the plasma reaction cavity and the product collection mode.
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