CN114057232A - One-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and preparation method thereof - Google Patents

One-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and preparation method thereof Download PDF

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CN114057232A
CN114057232A CN202111261388.7A CN202111261388A CN114057232A CN 114057232 A CN114057232 A CN 114057232A CN 202111261388 A CN202111261388 A CN 202111261388A CN 114057232 A CN114057232 A CN 114057232A
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邓勇辉
潘盼盼
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Abstract

The invention belongs to the technical field of advanced nano materials, and particularly relates to a one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and a preparation method thereof. The method takes magnetic nano particles as seeds, deposits a silicon dioxide layer on the surfaces of the particles by a sol-gel method and a magnetic field auxiliary assembly method, and then forms a one-dimensional rod core by directional arrangement and assembly under the induction of a stable magnetic field; adopting interface co-assembly, using a high molecular weight block copolymer as a template agent, and depositing a macromolecular surfactant/macromolecular layer composite material on the surface of the one-dimensional rod core; and then calcining at high temperature in inert atmosphere to form a one-dimensional ordered large mesoporous carbon material layer with an ordered mesostructure on the surface of the silicon dioxide. The one-dimensional nanorod has ordered large mesopores, a stable structure, a controllable mesostructure, unique magnetic anisotropy and spontaneous shearing and stirring of a one-dimensional magnetic material, and is simple in preparation method, high in yield, easy in obtaining of synthetic raw materials and suitable for large-scale production.

Description

One-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and preparation method thereof
Technical Field
The invention belongs to the technical field of advanced nano materials, and particularly relates to a one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and a preparation method thereof.
Background
The ordered mesoporous material is a novel nano material, has regular mesoporous channels, has an adjustable mesoporous channel structure, a high specific surface area, a large pore volume and rich components, not only expands the molecular sieve from micropores to mesopores, but also can be applied to macromolecule adsorption, catalytic reaction, drug storage, transportation and the like. The magnetic particles are widely applied to the fields of catalysis, contrast agents, targeted therapy and the like due to the special physicochemical properties. In the field of crossing the two, the combination of the ordered mesoporous material and the magnetic particles prepares the core-shell structure material with the magnetic particle core and the mesoporous shell, and exerts the advantages that other materials do not have.
In the prior art, the core-shell magnetic mesoporous material is usually based on a single silicon-based shell structure, and the application of the core-shell magnetic mesoporous material is severely limited. The core-shell magnetic mesoporous material composed of the hard carbon shell shows high chemical stability, good conductivity, photothermal effect, affinity with organic matters and the like, and can be widely applied to different subjects. Meanwhile, compared with zero-dimensional materials such as nano particles, microspheres and the like, the one-dimensional magnetic mesoporous material also has the unique advantages of anisotropy, adjustable length-diameter ratio, spontaneous shearing and stirring by applying a dynamic magnetic field and the like. However, how to realize precise control of each parameter of the one-dimensional magnetic mesoporous material is still a difficult problem to be solved urgently.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a one-dimensional core-shell magnetic ordered mesoporous carbon nanorod with unique structure, excellent performance and wide application and a preparation method thereof.
The one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod provided by the invention is a core-shell magnetic large mesoporous material consisting of a carbon shell, and has the characteristics of high chemical stability, good conductivity, photothermal effect, organic matter affinity and the like; the prepared one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod has the characteristics of ordered large mesopores, strong hydrophobicity, stable structure, high specific surface area and pore volume, controllable mesostructure, unique magnetic anisotropy and spontaneous shearing and stirring of one-dimensional magnetic materials, easy material transmission and diffusion, wide application prospect in the fields of electrochemistry, catalysis and the like, and can be widely applied to different disciplines; and the preparation method is simple, the yield of the method is high, the synthetic raw materials are easy to obtain, and the method is suitable for large-scale production.
The invention provides a one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod, which comprises: the magnetic nano-particles are deposited on the surface of the magnetic nano-particles, and the one-dimensional ordered large mesoporous material layer is arranged outside the silicon dioxide layer, wherein the magnetic nano-particles deposited with the silicon dioxide layer are directionally arranged and form a one-dimensional rod core, and the one-dimensional ordered large mesoporous material layer forms an ordered mesostructure outside the silicon dioxide layer of the one-dimensional rod core.
Preferably, the magnetic nanoparticles are prepared by a hydrothermal method, are uniform in size, have a particle size of 50 nm-800 nm, are highly dispersed in a polar solvent, and have strong paramagnetism; the material of the magnetic nanoparticles is selected from Fe3O4、CuFe2O4、γ-Fe2O3、NiFe2O4And one or more of magnetic substances such as nickel, iron, cobalt and the like.
Preferably, the silicon dioxide layer is a compact thin layer with the thickness of 10 nm-500 nm.
Preferably, the one-dimensional ordered mesoporous material layer outside the silicon dioxide layer is a polymer layer/carbon layer, the mesoporous aperture size is 10 nm-550 nm, the magnetism is 10 emu/g-80 emu/g, and the specific surface area is 100 m2/g~600 m2Per g, pore volume of 0.1 cm3/g~0.9 cm3The vertical radial thickness is 20nm to 500 nm. The formed ordered mesostructure comprises a mesoporous structure of vertically divergent tubular pore canals, spherical pore canals and/or vermicular pore canals; the space group of the pore channel structure is
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One or more of. The ordered large mesoporous carbon layer shows strong hydrophobic property.
Furthermore, the length of the formed one-dimensional nano rod is 2-20 μm.
The preparation method of the one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod provided by the invention comprises the following specific steps:
and step A, taking the magnetic nano particles as seeds, depositing a silicon dioxide layer on the surfaces of the magnetic nano particles, and then directionally arranging and assembling the magnetic nano particles under the induction of a stable magnetic field to form the one-dimensional rod core.
In the step, the magnetic nanoparticles are prepared by a hydrothermal method, have uniform size and particle size of 50-800 nm, are highly dispersed in a polar solvent, and have strong paramagnetism; the magnetic nano material is selected from Fe3O4、CuFe2O4、γ-Fe2O3、NiFe2O4And one or more of magnetic substances such as nickel, iron, cobalt and the like.
Depositing a silicon dioxide layer on the surface of the magnetic nano particles, and depositing a compact silicon dioxide thin layer on the surface of the magnetic nano particles by a sol-gel method; wherein, the silicon source used in the sol-gel method is selected from one or more of tetraethyl orthosilicate (TEOS), methyl orthosilicate (TMOS) and sodium silicate; in the process of synthesizing the compact silicon dioxide thin layer, the catalyst used for hydrolyzing the silicon source precursor is an acidic or basic catalyst; the alkaline catalyst is selected from one or more of sodium hydroxide, potassium hydroxide and concentrated ammonia water; the acid catalyst is selected from one or more of acetic acid, acetic acid and dilute hydrochloric acid; the used solvent is a mixed solution of alkyl alcohol and water; the alkyl alcohol is selected from one or more of methanol, ethanol or isopropanol; the mass ratio of alkyl alcohol to water is 9: 1-1: 9.
the one-dimensional rod core is formed by directional arrangement and assembly under the induction of a stable magnetic field, the adopted magnetic field is a static magnetic field, and the static magnetic field intensity is 2 mT-200 mT; the magnetic field induction time is 30-300 s; in a system assembled by directional arrangement, the mass percent of the magnetic nano particles is 0.01-1 wt.%, the mass percent of the silicon source is 0.2-2 wt.%, the mass percent of the catalyst is 1-10 wt.%, and the rest is an alcohol/water mixed solvent.
And step B, depositing a surfactant/polymer skeleton composite material layer on the surface of the silicon dioxide of the one-dimensional rod core by adopting an emulsion-assisted interface co-assembly method and using a surfactant, a pore-expanding agent, a carbon source and a catalyst as a template agent under an alkaline condition.
In the emulsion-assisted interfacial co-assembly method, an organic carbon precursor solution is used as a carbon source to form a polymer skeleton, and the carbon source precursor in the organic carbon precursor solution is selected from one or more of dopamine hydrochloride, a prepolymer of phenol and formaldehyde, a prepolymer of resorcinol and formaldehyde, tannic acid and derivatives thereof; the catalyst used for hydrolyzing the carbon source precursor is an acidic or basic catalyst; the alkaline catalyst is selected from one or more of sodium hydroxide, potassium hydroxide and concentrated ammonia water; the acidic catalyst is selected from one or more of acetic acid, acetic acid and dilute hydrochloric acid.
In the step, the surfactant is a non-ionic block copolymer EOnPOmEOn (n =20-132, m = 47-70) with large molecular weight, PEO-b-PS(Mw=10000-40000)、PS-b-P4VB(Mw=10000-40000)、PS-b-P2VB(Mw=10000-40000)、PEO-b-one or more of PMMA (Mw = 10000-; the solvent is mixed solution of alkyl alcohol, water and tetrahydrofuran, wherein the alkyl alcohol is selected from one or more of methanol, ethanol or isopropanol. The mass ratio of alkyl alcohol to water is 9: 1-1: 9, the volume ratio of the total mass of the hydroalcoholic to the tetrahydrofuran is 9: 1-1: 9.
in the step, in the interfacial co-assembly synthesis system of the surfactant/polymer skeleton composite material layer, the mass percent of the carbon source is 0.06 wt.% to 6 wt.%, the mass percent of the pore-expanding agent is 0.2 wt.% to 2 wt.%, the mass percent of the template agent is 0.2 wt.% to 2 wt.%, the mass percent of the catalyst is 0.2 wt.% to 2 wt.%, and the balance is alcohol and water, or a mixed solvent of alcohol, water and tetrahydrofuran.
And step C, calcining and carbonizing the composite material layer in an inert atmosphere to form an ordered large mesoporous carbon layer with an ordered mesostructure on the surface of the silicon dioxide to obtain the one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod.
In a preferred embodiment of the invention, in the step C, the one-dimensional magnetic ordered macroporous carbon nanorods with different hydrophobic functional surfaces are obtained by calcining and carbonizing in an inert atmosphere (the calcining temperature is 300 ℃ to 1100 ℃ and the calcining time is 1h to 8 h). And obtaining a one-dimensional ordered large mesoporous carbon material layer with an ordered mesostructure, wherein the ordered mesostructure comprises mesoporous, spherical mesoporous and vermicular mesoporous channels which are vertical to the radial direction and are scattered outwards, and functionalized surfaces with different hydrophobicity are obtained by adjusting different calcining temperatures and different functional groups on the surface of the mesoporous material layer.
In the step, the length of the obtained one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod is 2-20 microns, and the length is regulated and controlled by regulating the static magnetic field intensity and the magnetic field induction time; the diameter of the one-dimensional nano rod in the vertical direction is 100 nm-2 mu m, and the particle size of the magnetic nano particles, the thickness of the compact silicon dioxide layer and the concentration of an outer carbon source are regulated and controlled; the mesoporous aperture size of the one-dimensional nano rod is 5nm to 40 nm, the magnetism is 10 emu/g to 80 emu/g, and the specific surface area is 100 m2/g~600 m2Per g, pore volume of 0.1 cm3/g~0.9 cm3And/g is regulated and controlled by regulating the chain length of different templates, the concentration of a carbon source, the concentration of a pore-expanding agent and the concentration of magnetic nanoparticles. The controllable ordered mesostructure is obtained by regulating and controlling the parameters.
In the step, the pore-expanding agent is selected from one or more of 1,3, 5-trimethylbenzene, n-hexane and n-decane.
The invention has the following beneficial effects:
the invention provides a one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and a preparation method thereof.A magnetic nanoparticle is taken as a seed, a sol-gel method and a magnetic field auxiliary assembly method are combined, firstly, a silicon dioxide thin layer is deposited on the surface of the magnetic nanoparticle, and then the magnetic nanoparticle is directionally arranged and assembled under the induction of a stable magnetic field to form the one-dimensional nanorod; adopting an interface co-assembly technology, using a high molecular weight block copolymer as a template agent, and depositing a macromolecular surfactant/macromolecular layer composite material with an ordered mesostructure on the surface of silicon dioxide; and finally, calcining and carbonizing in an inert atmosphere to obtain the one-dimensional magnetic ordered large mesoporous carbon nano rod with the functionalized surfaces with different hydrophobicity. The one-dimensional nanorod provided by the invention has the characteristics of ordered large mesopores, stable structure, hydrophobic functionalized surface, controllable mesostructure, unique magnetic anisotropy and spontaneous shearing and stirring of a one-dimensional magnetic material, easiness in material transmission and diffusion, and wide application prospect in the fields of electrochemistry, catalysis and the like; and the preparation method is simple, the yield of the method is high, the synthetic raw materials are easy to obtain, and the method is suitable for large-scale production. The hard carbon shell used for forming the nano rod has high chemical stability, good conductivity, photothermal effect, affinity with organic matters and the like, and can be widely applied to different disciplines.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a TEM morphology of a one-dimensional core-shell magnetically ordered large mesoporous carbon nanorod in example 1 of the present invention;
FIG. 2 is a TEM morphology of a one-dimensional core-shell magnetically ordered large mesoporous carbon nanorod in example 2 of the present invention;
FIG. 3 is a TEM morphology of one-dimensional core-shell magnetically ordered large mesoporous carbon nanorods in example 3 of the present invention;
FIG. 4 is a TEM morphology of the one-dimensional core-shell magnetically ordered large mesoporous carbon nanorods in example 4 of the present invention.
Detailed Description
Through careful research, the inventor of the application discovers that the one-dimensional magnetic mesoporous material is prepared by adopting a magnetic field assisted assembly method, the preparation process has mild conditions and simple process. For example, under the condition of applying a static magnetic field, magnetic particles are firstly prepared into a one-dimensional ordered array by magnetic dipoles; and then, in order to effectively stabilize the material framework, a functional coating is coated on the surface of the material framework, and the functional coating is favorable for group functional modification and controllable deposition of a large mesoporous shell layer. However, how to realize precise control of the mesostructure, morphology and other aspects of the one-dimensional magnetic large mesoporous carbon material is still a difficult problem to be solved urgently when the one-dimensional magnetic large mesoporous carbon material is compounded with other materials and how to control each parameter.
It should be noted that the above prior art solutions have defects which are the results of practical and careful study by the inventors, and therefore, the discovery process of the above problems and the solutions proposed by the following embodiments of the present invention to the above problems should be the contribution of the inventors to the present invention in the course of the present invention.
The technical problems, aspects and advantages of the invention will be explained in detail below with reference to exemplary embodiments. The following exemplary embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1:
the embodiment provides a one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and a preparation method thereof.
The preparation method of the one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod comprises the following steps:
step A, 50 mg of magnetic ferroferric oxide particles with the particle size of about 50nm are added into 90 mL of ethanol for ultrasonic dispersion, mechanically stirred for 30 min at 350 rpm and rapidly added into 4.5 mL of strong ammonia water (28 wt.%); the speed was immediately increased to 700 rpm and stirred vigorously for 10 min, then the speed was adjusted back to 350 rpm and 0.45 mL TEOS was added dropwise and stirring was stopped after 15 min at 350 rpm. Then, the mixture is kept still in a stable magnetic field (15 mT) for 90 s, then the magnetic field is removed, after the mixture is kept still for 8 hours, magnetic nanorods of which the surfaces are deposited with a layer of silicon dioxide are obtained, the product is separated by a magnet and washed by a mixed solution of ethanol and water, and the washed product is dried at room temperature for later use.
In the step, the length of the magnetic nanorod is regulated and controlled by selecting the magnetic field intensity and the magnetic field induction time, and the length of the nanorod obtained under the current parameters is 2.6 microns. Meanwhile, the magnetic field induction time is related to the thickness of the silicon dioxide layer. In this example, the thickness of the deposited dense silica layer was 45 nm.
And step B, ultrasonically dispersing the one-dimensional magnetic ferroferric oxide nano rod with the surface deposited with a layer of compact silicon dioxide into a mixed solvent containing 40 mL of ethanol, 40 mL of deionized water and 0.96 g F127, then ultrasonically dispersing 1.0 mL of 1,3, 5-Trimethylbenzene (TMB) serving as a pore-expanding agent into the solution, adding 0.3 g of dopamine hydrochloride into the solution, stirring for 20 min to make the solution uniform, dropwise adding 0.5 mL of concentrated ammonia water, continuously and quickly stirring for 2h after complete dropwise addition to obtain the magnetic ferroferric oxide/macromolecular skeleton nano rod containing the macromolecular surfactant, collecting the product by using a magnet, and washing by using a mixed solution of ethanol and water. In the step, the carbon source is dopamine hydrochloride, and the vertical radial diameter of the magnetic nanoparticles is controlled by adjusting the particle size of the magnetic nanoparticles, the thickness of the compact silica layer and the concentration of the carbon source. Under the current parameters, a vertical radial diameter of 326nm was obtained. Meanwhile, the mesoporous aperture size, magnetism, specific surface area and pore volume of the nanorod are regulated and controlled by regulating the chain length of different templates, the concentration of a carbon source, the concentration of a pore expanding agent and the concentration of magnetic nanoparticles.
And step C, calcining and carbonizing the obtained nanorods at 300 ℃ for 1h and 550 ℃ for 2h in an inert atmosphere to obtain the one-dimensional core-shell magnetic ordered large mesoporous carbon nanorods.
The one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod prepared by the process comprises magnetic nanoparticles, a silicon dioxide layer deposited on the surface of the magnetic nanoparticles and a one-dimensional ordered mesoporous carbon-based material outside the silicon dioxide layer, wherein the magnetic nanoparticles deposited with the silicon dioxide layer are directionally arranged to form a one-dimensional rod core, the one-dimensional ordered mesoporous material layer forms an ordered mesostructure outside the silicon dioxide layer of the one-dimensional rod core, the ordered mesostructure comprises mesopores which are vertical to the radial direction and are outwards dispersed, carbon molecules are uniformly distributed on the surface of the large mesopores based on an ordered large mesoporous carbon layer formed by the rod core, the hydrophobic property is obtained from the carbon molecules and the structure of the large mesopores, and a functional surface with stronger hydrophobic property is obtained through the ordered mesoporous carbon layer. As shown in FIGS. 1 to 3, the magnetic saturation intensity is 30.6 emu/g, the nanorod length is 2.8 μm, the vertical radial diameter is 306nm, and the mesoporous diameter is 17.2 nm.
Example 2:
the embodiment also provides a one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and a preparation method thereof.
The preparation method of the one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod comprises the following steps:
step A, 50 mg of magnetic gamma-ferric oxide particles with the particle size of about 200nm are added into 60 mL of ethanol for ultrasonic dispersion, mechanically stirred at 350 rpm for 30 min, and rapidly added into 6 mL of strong ammonia water (28 wt.%); the speed was immediately increased to 700 rpm and stirred vigorously for 10 min, then the speed was adjusted back to 350 rpm and 0.9 mL TEOS was added dropwise and stirring was stopped after 15 min at 350 rpm. Then, the mixture is kept still in a stable magnetic field (30 mT) for 90 s, then the magnetic field is removed, after the mixture is kept still for 8 hours, magnetic nanorods of which the surfaces are deposited with a layer of silicon dioxide are obtained, the product is separated by a magnet and washed by a mixed solution of ethanol and water, and the washed product is dried at room temperature for later use.
And step B, ultrasonically dispersing the one-dimensional magnetic ferroferric oxide nano rod with the surface deposited with a layer of compact silicon dioxide in a mixed solvent containing 30 mL of ethanol, 60 mL of deionized water, 30 mL of tetrahydrofuran and 1.24 g P123, then ultrasonically dispersing 1.2 mL of 1,3, 5-Trimethylbenzene (TMB) into the solution, adding 0.5 g of dopamine hydrochloride into the solution, stirring for 20 min to make the solution uniform, dropwise adding 0.7 mL of concentrated ammonia water, continuously and rapidly stirring for 2h after dropwise adding is completed to obtain the magnetic ferroferric oxide/macromolecular skeleton nano rod containing the macromolecular surfactant, collecting the product by using a magnet, and washing by using a mixed solution of ethanol and water.
And step C, calcining the obtained nano rod in an inert atmosphere at the temperature of 600 ℃ for 2h for carbonization treatment to obtain the one-dimensional core-shell magnetic ordered large mesoporous carbon nano rod.
The one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod prepared by the process has the same structure as the one-dimensional nanorod in the embodiment 1, the magnetic saturation intensity is 38.7 emu/g, the nanorod length is 4.9 mu m, the vertical radial diameter is 420 nm, and the mesoporous aperture is 11.2 nm.
Example 3:
the embodiment also provides a one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and a preparation method thereof.
The preparation method of the one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod comprises the following steps:
step A, 50 mg of magnetic NiFe with the grain diameter of about 500nm2O4Adding the particles into 90 mL of ethanol, performing ultrasonic dispersion, mechanically stirring at 350 rpm for 30 min, and quickly adding into 9 mL of concentrated ammonia water (28 wt.%); the speed was immediately increased to 700 rpm and stirred vigorously for 10 min, then the speed was adjusted back to 350 rpm and 0.9 mL TEOS was added dropwise and stirring was stopped after 15 min at 350 rpm. Then, standing in a stable magnetic field (60 mT) for 180 s, removing the magnetic field, standing for 8 h to obtain magnetic nanorods with a layer of silicon dioxide deposited on the surface, separating the product with a magnet, washing with a mixed solution of ethanol and water, and drying the washed product at room temperature for later use.
And step B, ultrasonically dispersing the one-dimensional magnetic ferroferric oxide nano rod with the surface deposited with the layer of compact silicon dioxide in a mixed solvent containing 40 mL of ethanol, 40 mL of deionized water and 1.24 g F127, then ultrasonically dispersing 0.9 mL of n-hexane into the solution, adding 2.0 g of dopamine hydrochloride into the solution, stirring for 20 min to make the solution uniform, dropwise adding 1.4 mL of concentrated ammonia water, continuously and rapidly stirring for 2h after dropwise adding is completed to obtain the magnetic ferroferric oxide/macromolecular skeleton nano rod containing the macromolecular surfactant, collecting the product by using a magnet, and washing by using a mixed solution of ethanol and water.
And step C, calcining the obtained nano rod for 3 h carbonization at 450 ℃ in an inert atmosphere to obtain the one-dimensional core-shell magnetic ordered large mesoporous carbon nano rod with the weaker hydrophobic surface.
The one-dimensional core-shell magnetically ordered large mesoporous carbon nanorod prepared by the above process has the same structure as the one-dimensional nanorod of example 1, and as shown in fig. 4, the magnetic saturation intensity is 48.2 emu/g, the nanorod length is 8.2 μm, the vertical radial diameter is 618nm, and the mesoporous diameter is 13.4 nm.
Example 4:
the embodiment also provides a one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod and a preparation method thereof.
The preparation method of the one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod comprises the following steps:
step A, 50 mg of magnetic ferroferric oxide particles with the particle size of about 800nm are added into 60 mL of ethanol for ultrasonic dispersion, mechanically stirred for 30 min at 350 rpm and rapidly added into 12 mL of strong ammonia water (28 wt.%); the speed was immediately increased to 700 rpm and stirred vigorously for 10 min, then the speed was adjusted back to 350 rpm and 1.5 mL TEOS was added dropwise and stirring was stopped after 15 min at 350 rpm. Then, the mixture is kept still in a stable magnetic field (80 mT) for 300 s, then the magnetic field is removed, the mixture is kept still for 8 h to obtain magnetic nanorods, a layer of silicon dioxide is deposited on the surfaces of the magnetic nanorods, the product is separated by a magnet and washed by a mixed solution of ethanol and water, and the washed product is dried at room temperature for later use.
Step B, ultrasonically dispersing the one-dimensional magnetic ferroferric oxide nano-rod with the surface deposited with the layer of the compact silicon dioxide into a solution containing 60 mL of ethanol, 30 mL of deionized water, 30 mL of tetrahydrofuran and 0.5 g of PEO-b-PS (Mn = 35421g·mol−1) Then 1.2 mL of 1,3, 5-Trimethylbenzene (TMB) is ultrasonically dispersed into the solution, 1.0 g of dopamine hydrochloride is added into the solution, the solution is stirred for 20 min to be uniform, 2.0 mL of strong ammonia water is dropwise added, the solution is continuously and rapidly stirred for 2h after the dropwise addition is completed, the magnetic ferroferric oxide/macromolecular framework nanorod containing the macromolecular surfactant is obtained, and a product is collected by a magnet and washed by a mixed solution of ethanol and water.
And step C, calcining the obtained nano rod for 1h carbonization at 800 ℃ in an inert atmosphere to obtain the one-dimensional core-shell magnetic ordered large mesoporous carbon nano rod with the strong hydrophobic surface.
The one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod prepared by the process has the same structure as the one-dimensional nanorod in the embodiment 1, the magnetic saturation intensity is 63.9 emu/g, the nanorod length is 14.6 mu m, the vertical radial diameter is 720nm, and the mesoporous aperture is 15.8 nm.
While the foregoing is directed to the preferred embodiment of the present invention, it is understood that the invention is not limited to the exemplary embodiments disclosed, but is made merely for the purpose of providing those skilled in the relevant art with a comprehensive understanding of the specific details of the invention. It will be apparent to those skilled in the art that various modifications and adaptations of the present invention can be made without departing from the principles of the invention and the scope of the invention is to be determined by the claims.

Claims (10)

1. A one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod is characterized by comprising: the magnetic nano particle comprises a magnetic nano particle, a silicon dioxide layer deposited on the surface of the magnetic nano particle, and a one-dimensional ordered large mesoporous carbon-based material layer outside the silicon dioxide layer; the magnetic nano particles deposited with the silicon dioxide layer are arranged directionally to form a one-dimensional rod core, the one-dimensional ordered large mesoporous carbon-based material layer forms an ordered mesostructure outside the silicon dioxide layer of the one-dimensional magnetic core, and strong hydrophobicity is obtained through the ordered mesostructure carbon-based material layer.
2. The one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod according to claim 1, wherein the one-dimensional ordered large mesoporous carbon-based material layer outside the silicon dioxide layer has a mesoporous size of 10nm to 550 nm, a magnetic property of 10 emu/g to 80 emu/g, and a specific surface area of 100 m2/g~600 m2Per g, pore volume of 0.1 cm3/g~0.9 cm3The vertical radial thickness is 20nm to 500 nm.
3. The one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod according to claim 1, wherein the formed ordered mesostructure comprises a mesoporous structure of vertically divergent tubular channels, spherical channels and/or vermicular channels; pore structure thereofOn the space group is
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One or more of.
4. A preparation method of one-dimensional core-shell magnetic ordered large mesoporous carbon nanorods based on any one of claims 1 to 3, the preparation method comprising the steps of:
step A, taking magnetic nano particles as seeds, depositing a silicon dioxide layer on the surfaces of the magnetic nano particles, and then directionally arranging and assembling the magnetic nano particles under the induction of a stable magnetic field to form a one-dimensional rod core;
b, adopting an emulsion-assisted interface co-assembly method, under an alkaline condition, carrying out the fusion of composite micelles and the polymerization of an organic carbon source on the surface of the silicon dioxide of the one-dimensional rod core in a synergistic manner by using an amphiphilic surfactant as a template agent and the emulsification induction of organic micromolecules as a pore expanding agent and an interface regulator, and depositing a surfactant/polymer skeleton composite material layer;
and step C, carrying out calcination carbonization treatment on the composite material layer in an inert atmosphere to form an ordered large mesoporous carbon material layer with an ordered mesostructure on the surface of the silicon dioxide, so as to obtain the one-dimensional magnetic ordered large mesoporous carbon nanorods with different surface hydrophobic capabilities.
5. The preparation method of the one-dimensional core-shell magnetic ordered macroporous carbon nanorod according to claim 4, wherein the magnetic nanoparticles are prepared by a hydrothermal method, have the particle size of 50 nm-800 nm, are highly dispersed in a polar solvent, and have strong paramagnetism.
6. The preparation method of the one-dimensional core-shell magnetically ordered macroporous carbon nanorod according to claim 4, wherein the step A is directionally arranged and assembled under the induction of a stable magnetic field to form the one-dimensional rod core, the adopted magnetic field is a static magnetic field, the static magnetic field strength is 2 mT-200 mT, and the magnetic field induction time is 30 s-300 s.
7. The preparation method of the one-dimensional core-shell magnetic ordered large mesoporous carbon nanorod according to claim 4, wherein in a system assembled in an oriented arrangement manner, the mass percent of the magnetic nanoparticles is 0.01-1 wt.%, the mass percent of the silicon source is 0.2-2 wt.%, the mass percent of the catalyst is 1-10 wt.%, and the rest is an alcohol/water mixed solvent.
8. The method for preparing one-dimensional core-shell magnetic ordered macroporous carbon nanorods according to claim 4, wherein the surfactant is a non-ionic block copolymer with large molecular weight EOnPOmEOn with n =20-132, m =47-70, PEO-b-PS and Mw =10000-b-P4VB and Mw =10000-b-P2VB and Mw =10000-b-PMMA and Mw = 10000-.
9. The preparation method of the one-dimensional core-shell magnetically ordered macroporous carbon nanorod according to claim 4, wherein in an interface co-assembly synthesis system of the surfactant/polymer skeleton composite material layer, the mass percentage of the carbon source is 0.06 wt.% to 6 wt.%, the mass percentage of the pore-expanding agent is 0.2 wt.% to 2 wt.%, the mass percentage of the templating agent is 0.2 wt.% to 2 wt.%, the mass percentage of the catalyst is 0.2 wt.% to 2 wt.%, and the balance is alcohol and water, or a mixed solvent of alcohol, water and tetrahydrofuran.
10. The preparation method of the one-dimensional core-shell magnetically ordered macroporous carbon nanorod according to claim 4, wherein the length of the nanorod is 2-20 μm, and the length is regulated and controlled by adjusting the magnetic field intensity and the magnetic field induction time; the diameter of the nano rod in the vertical direction is 100 nm-2 mu m, and the particle size of the magnetic nano particles, the thickness of the silicon dioxide layer and the concentration of a carbon source are regulated and controlled; the mesoporous aperture size of the nano rod is 10 nm-50 nm, the magnetism is 10 emu/g-80 emu/g, and the specific surface area is 100 m2/g~600 m2Per g, pore volume of 0.1 cm3/g~ 0.9cm3The concentration of the magnetic nanoparticles is controlled by adjusting the chain length of the template agent, the concentration of the carbon source, the concentration of the pore expanding agent and the concentration of the magnetic nanoparticles; the hydrophobic functional surface of the nano rod is regulated and controlled by regulating the calcining temperature and the functional group on the surface of the mesoporous layer material.
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