CN112110492A - Magnetic halloysite nanotube and preparation method and application thereof - Google Patents
Magnetic halloysite nanotube and preparation method and application thereof Download PDFInfo
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 80
- 239000002071 nanotube Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 12
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 9
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 9
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000007898 magnetic cell sorting Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
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Abstract
The invention discloses a preparation method of a magnetic halloysite nanotube, which comprises the following steps: by adopting an organic iron method, the halloysite nanotube is taken as a nano container, dispersed in organic iron solution and reacted in an oxygen-free environment, and ferroferric oxide nano particles are synthesized in situ in the halloysite nanotube, so that the magnetic halloysite is formed. The preparation method of the magnetic halloysite is simple, the raw material source is rich, and the cost is low; meanwhile, the surface property of the halloysite is not changed by the magnetic halloysite, and the magnetic halloysite can be subjected to various surface modifications and applied to the fields of biomedicine, chemistry, environmentality and the like.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a magnetic halloysite nanotube and a preparation method and application thereof.
Background
The magnetic nano-particle has wide application in the biomedical fields of drug carriers, magnetic separation, cell sorting and the like due to the unique size effect and magnetic responsiveness. Fe3O4The nano particles become the most widely applied magnetic nano particles in the biomedical field due to the higher saturation magnetization and the biosafety that the nano particles can be regularly discharged out of the body. But the surface free energy is lower, the dipole effect among particles is stronger, the stability is lower, the agglomeration is easy, and the surface modification method has certain specificity, and the superior characteristics are difficult to be fully exerted in practical application.
The halloysite nanotube can be regarded as kaolinite with a special structure formed under natural conditions, 15-20 layers of kaolinite Al/Si sheets are curled, and a multi-wall nanotube with bound water is arranged between layers, wherein the inner diameter of a tube cavity is 10-15nm, the outer diameter is 50-70nm, and the length is 1.0-1.5 mu m. In the environment with pH value of 1.5-8.5, the outer surface of the halloysite nanotube Si-O structure is electronegative, and the inner surface of the Al-OH structure is electropositive. Unlike sheet clay materials such as montmorillonite, kaolin, bentonite, etc., halloysite has a great advantage in that it can be well dispersed in water and polar polymers without being exfoliated, and surface modification can be easily performed by using its surface structure characteristics. Modifying nanoparticles, e.g. Au, Ag, Ni, MnO, in halloysite nanotube lumens2The metal particles are endowed with functional applications such as halloysite catalysis and imaging, so that the halloysite can be used for preparing functional composite materials. Although the outer surface of the halloysite nanotube is modified with Fe3O4The research of the nano particles has been reported, but the method occupies the outer surface with unique properties of the halloysite nano tube, and limits the application of secondary functionalization of the surface.
Therefore, how to provide a preparation method of magnetic halloysite nanotubes with easy surface secondary functionalization is a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the invention takes a halloysite natural nanotube as a nano container, and synthesizes ferroferric oxide nano particles in situ in a tube cavity of the nano container to obtain a method for further surface functionalization modification of a magnetic halloysite nanotube.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a magnetic halloysite nanotube, which is used for in-situ synthesis of magnetic nanoparticles in the halloysite nanotube by an organic iron method, and comprises the following steps:
(1) preparing an organic iron solution: dissolving ferric acetylacetonate in a solvent to obtain an organic iron solution;
(2) adding the halloysite nanotube into an organic iron solution, transferring the halloysite nanotube into a three-neck flask, and uniformly mixing;
(3) vacuumizing the three-neck flask, and introducing nitrogen to ensure that the reaction system is completely in a nitrogen atmosphere;
(4) when the nitrogen is completely filled in the whole system, cooling water is introduced, the mixture is stirred and heated to 230 ℃ and kept at the constant temperature for 10-50min, then the temperature is raised to 300 ℃ and heated and refluxed for 10-50 min; (ii) a
(5) And after the reaction is finished, stopping heating and stirring, cooling the black-brown mixture in the three-neck flask to room temperature, and centrifugally collecting a product to obtain a dark reddish brown precipitate, namely the magnetic halloysite nanotube.
Preferably, in the above method for preparing a magnetic halloysite nanotube, the solvent in step (1) is prepared from (15-13): (2-1.5): (1.5-1.01) diphenyl ether, 1, 2-hexadecanediol, oleic acid and oleylamine of 1.
The beneficial effects of the above technical scheme are: 1, 2-hexadecanediol in the mixed solvent is used as a reducing agent, oleic acid and oleylamine in the solvent can ensure good dispersion of the nano particles, and the particle size distribution of the formed ferroferric oxide nano particles is narrow.
Preferably, in the above method for preparing a magnetic halloysite nanotube, the amount of the ferric acetylacetonate added in step (1) is 1-5% by mass of the solvent.
The beneficial effects of the above technical scheme are: the particle size of the formed ferroferric oxide nano-particles is controlled by controlling the addition amount of the ferric acetylacetonate.
Preferably, in the above method for preparing a magnetic halloysite nanotube, the addition amount of the halloysite nanotube in the step (2) is 5-5000% of the addition amount of the iron acetylacetonate in the step (1). .
The beneficial effects of the above technical scheme are: the loading capacity of the ferroferric oxide nano particles is controlled by controlling the proportion of the halloysite nano tubes to the ferric acetylacetonate.
Preferably, in the above method for preparing a magnetic halloysite nanotube, the evacuation operation in step (3) is repeated 2-5 times, evacuation is performed for 15-45min each time, then 5-20min of evacuation is performed to recover the normal pressure state, and nitrogen is introduced after the last evacuation operation is completed.
The beneficial effects of the above technical scheme are: the mixed solution can easily enter the nanotube under the action of pressure difference, so that the air in the three-neck flask is better ensured, and the system is completely in the nitrogen atmosphere in the reaction process.
Preferably, in the above method for preparing a magnetic halloysite nanotube, the step (5) of centrifugally collecting the product specifically includes the following steps:
(1) under the condition of normal temperature environment, adding absolute ethyl alcohol into the black-brown mixture, uniformly mixing, centrifuging for 10-20min at the rotating speed of 8000r/min to obtain black precipitate, and removing supernatant;
(2) adding oleic acid, oleylamine and n-hexane into a centrifugal tube, oscillating to uniformly disperse black precipitates in an n-hexane system, centrifuging, and removing supernatant;
(3) and (3) repeating the centrifugation operation of the step (1) for 2-3 times on the precipitate to finally obtain a dark reddish brown precipitate, namely the magnetic halloysite nanotube.
Preferably, in the above method for preparing magnetic halloysite nanotubes, the addition amount of the absolute ethanol is 1-100 times of the volume of the dark-brown mixture during each centrifugation.
The beneficial effects of the above technical scheme are: sufficient ethanol is sufficient to dissolve and wash away unreacted starting materials.
Preferably, in the above method for preparing a magnetic halloysite nanotube, the addition amount of oleic acid is 1-100% of the volume of the black-brown mixture, the addition amount of oleylamine is 1-100% of the volume of the black-brown mixture, and the addition amount of n-hexane is 1-100 times of the volume of the black-brown mixture.
The beneficial effects of the above technical scheme are: n-hexane mixed with oleylamine and oleic acid can disperse the magnetic halloysite nanotubes well.
The magnetic halloysite nanotube is prepared by the method, and the magnetic halloysite nanotube modified antibody is used as a capture magnetic bead for detecting antigens or special nucleic acid sequences, and is applied to biological fields such as capture of biomolecules (proteins or nucleic acid molecules) and special cells, or is applied to separation of pollutants in sewage.
According to the technical scheme, compared with the prior art, the invention discloses a preparation method of a magnetic halloysite nanotube, wherein the magnetic halloysite nanotube is prepared by an organic iron method, and the magnetic halloysite nanotube prepared by the method maintains the surface chemical property of the original halloysite nanotube, can be further subjected to functionalized surface modification and is applied to the fields of biomedicine, chemistry, environmental science and the like, for example, the magnetic halloysite nanotube can be used as a capture magnetic bead after being modified with an antibody; the method can also be used for sewage treatment, and the magnetic property of the magnetic halloysite nanotube is utilized to separate pollutants.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a transmission electron microscope image of the magnetic halloysite nanotubes synthesized in example 1;
FIG. 2 is a hysteresis loop of the magnetic halloysite nanotubes synthesized in example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses a preparation method of a magnetic halloysite nanotube. The preparation process comprises the following steps: by an organic iron method, the halloysite nanotube is dispersed in an organic iron solution, reacts in an oxygen-free environment, and in-situ synthesizes magnetic nano iron oxide particles in the halloysite nanotube, so that the magnetic halloysite is formed. The preparation method of the magnetic halloysite is simple, the raw material sources are rich, and the cost is low. Meanwhile, the surface property of the halloysite is not changed by the magnetic halloysite, and the magnetic halloysite can be subjected to various modifications and applied to the fields of biomedicine, chemistry, environmentality and the like.
Example 1
A method for preparing a magnetic halloysite nanotube. The synthesis method comprises the following steps:
1) preparing an organic iron solution: 21.46g of diphenyl ether, 2.585g of 1, 2-hexadecanediol, 1.695g of oleic acid and 1.605g of oleylamine are mixed to be used as a solvent of organic iron, and then 0.7g of ferric acetylacetonate is added;
2) adding 0.1g of halloysite nanotubes into an organic iron solution, transferring the halloysite nanotubes into a three-neck flask, and uniformly mixing;
3) the three-neck flask was evacuated by a vacuum pump to remove air. In order to better ensure that no air exists in the three-neck flask, the system is vacuumized for 30min each time and then deflated for 15min to restore normal pressure operation, the vacuumizing operation is repeated for 3 times, and nitrogen is directly introduced after the last vacuumizing operation is finished, so that the system is completely in a nitrogen atmosphere;
4) and (3) introducing cooling water when the whole system is completely filled with nitrogen, starting magnetic stirring, heating the system, controlling the temperature when the mixture is heated to 200 ℃, keeping the temperature for 30 minutes, raising the temperature to 265 ℃, and heating and refluxing for 30 minutes. During the period, the boiling degree of the liquid in the three-neck flask needs to be always noticed, and the temperature is strictly controlled;
5) after the reaction was completed, heating and stirring were stopped, the heat source was removed, and the dark brown mixture in the three-necked flask was allowed to cool to room temperature.
The collection method of the product is carried out according to the following steps:
1) under the condition of normal temperature environment, adding 40ml of absolute ethyl alcohol into the mixture, uniformly mixing, and carrying out centrifugal operation at the rotating speed of 8000 revolutions per minute for 10min to obtain black precipitate;
2) pouring out supernatant liquid, adding about 0.05ml of oleic acid and 0.05ml of oleylamine into a centrifugal tube, adding a proper amount of n-hexane, and vibrating to well disperse black precipitates in the n-hexane system;
3) the solution is again subjected to the centrifugation operation of step 1) to remove any residues not dispersed;
4) adding a proper amount of absolute ethyl alcohol into the product again to precipitate the ferroferric oxide nano particles and remove the solvent;
5) and repeating the centrifugation operation for 3 times to finally obtain a dark reddish brown precipitate, namely the magnetic halloysite nanotube.
FIG. 1 shows a transmission electron microscope image of the synthesized magnetic halloysite nanotubes, and the hysteresis loop test of the synthesized magnetic halloysite nanotubes is performed, as shown in FIG. 2.
Example 2
A preparation method of a magnetic halloysite nanotube comprises the following steps:
1) preparing an organic iron solution: mixing 25.5g of diphenyl ether, 3.1g of 1, 2-hexadecanediol, 1.85g of oleic acid and 1.8g of oleylamine to serve as a solvent of organic iron, and then adding 1g of ferric acetylacetonate;
2) adding 0.2g of halloysite nanotubes into an organic iron solution, transferring the halloysite nanotubes into a three-neck flask, and uniformly mixing;
3) vacuumizing the three-mouth flask by using a vacuum pump to remove air, in order to better ensure that no air exists in the three-mouth flask, vacuumizing the system for 30min each time, then deflating for 10min to recover normal pressure operation, repeating the vacuumizing operation for 4 times, directly introducing nitrogen after the last vacuumizing operation is finished, and ensuring that the system is completely in a nitrogen atmosphere;
4) and (3) introducing cooling water when the whole system is completely filled with nitrogen, starting magnetic stirring, heating the system, controlling the temperature when the mixture is heated to 200 ℃, and keeping for 30 min. Then the temperature is raised to 265 ℃ and heated to reflux for 30min, during which time the liquid in the three-neck flask is required to be constantly kept in the boiling degree and the temperature is strictly controlled.
5) After the reaction was completed, heating and stirring were stopped, the heat source was removed, and the dark brown mixture in the three-necked flask was allowed to cool to room temperature.
The collection method of the product is carried out according to the following steps:
1) under the condition of normal temperature environment, adding 30ml of absolute ethyl alcohol into the mixture, uniformly mixing, and carrying out centrifugal operation at the rotating speed of 8000 revolutions per minute for 15min to obtain black precipitate;
2) pouring out supernatant liquid, adding about 0.1ml of oleic acid and 0.1ml of oleylamine into a centrifugal tube, adding a proper amount of n-hexane, and vibrating to well disperse black precipitates in the n-hexane system;
3) the solution is again subjected to the centrifugation operation of step 1) to remove any residues not dispersed;
4) adding a proper amount of absolute ethyl alcohol into the product again to precipitate the ferroferric oxide nano particles and remove the solvent;
5) and repeating the centrifugation operation for 3 times to finally obtain a dark reddish brown precipitate, namely the magnetic halloysite nanotube.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed by the embodiment, the scheme corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a magnetic halloysite nanotube is characterized in that magnetic nanoparticles are synthesized in situ in the halloysite nanotube by an organic iron method, and the preparation method comprises the following steps:
(1) preparing an organic iron solution: dissolving ferric acetylacetonate in a solvent to obtain an organic iron solution;
(2) adding the halloysite nanotube into an organic iron solution, transferring the halloysite nanotube into a three-neck flask, and uniformly mixing;
(3) vacuumizing the three-neck flask, and introducing nitrogen to ensure that the reaction system is completely in a nitrogen atmosphere;
(4) when the whole system is completely filled with nitrogen, introducing cooling water, stirring and heating to 180-230 ℃, keeping the temperature for 10-50min, then raising the temperature to 250-300 ℃, and heating and refluxing for 10-50 min;
(5) and after the reaction is finished, stopping heating and stirring, cooling the black-brown mixture in the three-neck flask to room temperature, and centrifugally collecting a product to obtain a dark reddish brown precipitate, namely the magnetic halloysite nanotube.
2. The method for preparing the magnetic halloysite nanotubes according to claim 1, wherein the solvent in the step (1) is prepared from the following components in a mass ratio of (15-13): (2-1.5): (1.5-1.01) diphenyl ether, 1, 2-hexadecanediol, oleic acid and oleylamine of 1.
3. The method for preparing magnetic halloysite nanotubes according to claim 1 or 2, wherein the amount of ferric acetylacetonate added in step (1) is 1-5% by mass of the solvent.
4. The method for preparing magnetic halloysite nanotubes according to claim 1, wherein the amount of halloysite nanotubes added in step (2) is 5-5000% of the amount of ferric acetylacetonate added in step (1).
5. The method for preparing a magnetic halloysite nanotube according to claim 1, wherein the vacuumizing operation in step (3) is repeated 2-5 times, the vacuumizing operation is performed for 15-45min each time, then the air is released for 5-20min to recover the normal pressure state, and nitrogen is introduced after the last vacuumizing operation is completed.
6. The method for preparing magnetic halloysite nanotubes according to claim 1, wherein the step (5) of centrifugally collecting the product comprises the following steps:
(1) under the condition of normal temperature environment, adding absolute ethyl alcohol into the black-brown mixture, uniformly mixing, centrifuging for 10-20min at the rotating speed of 8000r/min to obtain black precipitate, and removing supernatant;
(2) adding oleic acid, oleylamine and n-hexane into a centrifugal tube, oscillating to uniformly disperse black precipitates in an n-hexane system, centrifuging, and removing supernatant;
(3) and (3) repeating the centrifugation operation of the step (1) for 2-3 times on the precipitate to finally obtain a dark reddish brown precipitate, namely the magnetic halloysite nanotube.
7. The method of claim 6, wherein the absolute amount of ethanol added during each centrifugation is 1-100 times the volume of the dark-brown mixture.
8. The method of claim 6, wherein the amount of oleic acid added is 1-100% by volume of the dark-brown mixture, the amount of oleylamine added is 1-100% by volume of the dark-brown mixture, and the amount of n-hexane added is 1-100 times by volume of the dark-brown mixture.
9. A magnetic halloysite nanotube prepared by the method of any one of claims 1-8.
10. Use of magnetic halloysite nanotubes prepared by the method of any one of claims 1 to 8 in biomedical, chemical, environmental fields, including modification of antibodies or specific nucleic acid sequences as capture magnetic beads for detection of antigens or specific nucleic acid sequences, capture of biomolecules, specific cells, and separation of contaminants in sewage.
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