CN114392727A - Magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material and preparation method thereof - Google Patents
Magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material and preparation method thereof Download PDFInfo
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- CN114392727A CN114392727A CN202111599171.7A CN202111599171A CN114392727A CN 114392727 A CN114392727 A CN 114392727A CN 202111599171 A CN202111599171 A CN 202111599171A CN 114392727 A CN114392727 A CN 114392727A
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 239000011258 core-shell material Substances 0.000 title claims abstract description 46
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000004094 surface-active agent Substances 0.000 claims abstract description 44
- 239000000693 micelle Substances 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 39
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- 238000005406 washing Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
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- 230000002378 acidificating effect Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims description 3
- 229910016516 CuFe2O4 Inorganic materials 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- 229910003264 NiFe2O4 Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 3
- FFOWIEZZYLIBTD-UHFFFAOYSA-N butan-2-olate zirconium(4+) Chemical compound CCC(C)O[Zr](OC(C)CC)(OC(C)CC)OC(C)CC FFOWIEZZYLIBTD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229920000359 diblock copolymer Polymers 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 3
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 11
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- 235000019441 ethanol Nutrition 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
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- 239000002122 magnetic nanoparticle Substances 0.000 description 3
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- 102000004190 Enzymes Human genes 0.000 description 1
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
Abstract
The invention relates to the technical field of functional material preparation, in particular to a magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material and a preparation method thereof, wherein the preparation method comprises the steps of firstly dissolving a shell precursor, a surfactant and a catalyst in an organic solvent to obtain a mixed solution; drying the mixed solution to obtain single micelle gel; dispersing the single micelle gel and the magnetic inorganic nano particles in an organic alcohol-water solution, heating, further hydrolyzing and crosslinking a precursor of a shell layer which is not completely hydrolyzed, and inducing the assembly of the single micelle on the surface of the inorganic nano particles; and finally, roasting at high temperature to remove the surfactant, thereby obtaining the magnetic inorganic nano-particle @ ordered mesoporous material core-shell composite material. The composite material has high specific surface area and strong magnetic responsiveness, and has wide application prospect in bioseparation and adsorption. The method is simple, the raw materials are easy to obtain, and the method is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of functional material preparation, in particular to a magnetic inorganic nanoparticle and ordered mesoporous material core-shell composite material and a preparation method thereof.
Background
In recent years, with the demands of biological analysis and separation, enzyme immobilization, and disease diagnosis, core-shell composite materials having magnetic particles as a core and mesoporous materials as a shell have attracted much attention. The composite material can have the magnetic response characteristic of magnetic nano particles and the characteristics of high specific surface, high pore volume, uniform mesoporous pore channels and the like of mesoporous materials, thereby realizing the purpose of simplifying and facilitating separation and analysis.
So far, the synthesis of core-shell composite nanospheres with magnetic nanoparticles as cores and mesoporous materials as shells has been reported (j.mater.chem.,2009,19, 6706; adv.mater, 2009,21, 1377; j.am.chem.soc., 2011,133,15830; j.am.chem.soc.,2010,132,8466; j.am.chem.soc.,2012,134,11864; j.am.chem.soc.,2015,137,13282; Nano res.,2015,8, 2503; j.mater.chem.a,2014,2, 18322; j.am.chem.soc.,2017,139,15486; j.am.chem.soc.,2017,139,4954), but some obvious disadvantages exist. Firstly, the synthesis steps are complex, a layer of dense silicon dioxide or polymer is required to be wrapped on the surface of the magnetic particles to ensure the uniform wrapping of the mesoporous shell layer, and the direct wrapping of the mesoporous shell layer on the surface of the magnetic particles is still very difficult; secondly, the preparation method has poor universality, most of the reported composite materials are concentrated on a silicon dioxide-based mesoporous shell layer, and the controllable construction of a carbon-based or oxide-based mesoporous shell layer on the surface of magnetic particles still has a challenge; thirdly, the composite material synthesized has a certain defect in the aspect of material transmission due to disordered mesopores or mesopores parallel to the surface of the microsphere.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material and a preparation method thereof, wherein the prepared core-shell structure composite material has the shell thickness (5-100nm), the composition (silicon dioxide, carbon, titanium dioxide, zirconium dioxide or aluminum oxide), the pore diameter (2-40nm), the mesostructure (P6mm, Fm3m, Im3m, Pm3n, Fd3m or Ia3d) and the specific surfaceProduct (50-1200 m)2The/g) is adjustable, and has the characteristics of high magnetic response, uniform shape, ordered mesopores and easy material transmission and diffusion. The thickness of the shell layer can be adjusted through the feeding ratio of the single micelle gel to the shell layer, the components can be adjusted through using different precursors, the pore diameter can be adjusted through using different types and amounts of surfactants, the mesostructure can be controlled through the feeding ratio between the surfactants and the precursors, and the specific surface area can be adjusted through the adding amount of the surfactants.
Different from various magnetic particle mesoporous core-shell composite materials reported previously, the invention provides a strategy of single micelle interface assembly for directly coating ordered mesoporous shell layers on the surfaces of magnetic particles. The method has strong universality and is suitable for a series of mesoporous shells with different components, including silicon dioxide, carbon, aluminum oxide, titanium dioxide, zirconium dioxide and the like. The core-shell structure composite material synthesized by the method has the characteristics of high magnetic response, uniform shape, ordered mesopores and easiness in material transmission and diffusion. Has important application prospect in the field of adsorption separation and is suitable for large-scale production.
The technical scheme of the invention provides a magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material and a preparation method thereof, firstly, a surfactant, a shell precursor and a catalyst are dissolved in an organic solvent, and the surfactant and the shell precursor are assembled through weak interaction along with the volatilization of the solvent to obtain a single micelle element; then, under the heating condition, the single micelle primitive is orderly assembled on the surface of the magnetic particle; and finally, roasting at high temperature to remove the surfactant, thereby obtaining the magnetic inorganic nano-particle and ordered mesoporous material core-shell composite material.
The purpose of the invention can be realized by the following technical scheme:
the invention aims to provide a preparation method of a magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material, which comprises the following steps:
(1) dissolving a surfactant, a shell precursor and a catalyst in an organic solvent to obtain a mixed solution;
(2) drying the mixed solution obtained in the step (1) to obtain single micelle gel;
(3) mixing the single micelle gel obtained in the step (2) with magnetic inorganic nano particles, organic alcohol and water, reacting, washing, drying and roasting a reaction product at a high temperature to obtain the magnetic inorganic nano particle @ ordered mesoporous material core-shell composite material;
wherein the specific surface area of the magnetic inorganic nano-particle @ ordered mesoporous material core-shell composite material is 50-1200m2The mesoporous size is 2-40nm, and the thickness of a mesoporous shell layer is 5-100 nm;
the ordered mesoporous material is selected from one of silicon dioxide, carbon, titanium dioxide, zirconium dioxide or aluminum oxide; the space group of the mesostructure of the ordered mesoporous material is one or a mixture of more of P6mm, Fm3m, Im3m, Pm3n, Fd3m or Ia3 d.
In one embodiment of the present invention, in step (1), the surfactant is selected from one or more of an anionic surfactant, a cationic surfactant or a nonionic surfactant;
the anionic surfactant is selected from one or more of glutamic acid anionic surfactant, alanine anionic surfactant, glycine anionic surfactant or carboxylic acid anionic surfactant;
the cationic surfactant is selected from one or more of alkyl quaternary ammonium salt surfactant, gemini surfactant, meteor hammer surfactant or three-head cationic surfactant;
the nonionic surfactant is selected from one or more of polyethylene oxide-polypropylene oxide, polyethylene oxide-polybutylene oxide, polyethylene oxide-polystyrene or polyethylene oxide-polymethyl methacrylate diblock copolymer, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and polypropylene oxide-polyethylene oxide-polypropylene oxide triblock copolymer.
In one embodiment of the present invention, in the step (1), the shell layer precursor is selected from one of tetraethyl orthosilicate, sodium silicate, tetramethyl orthosilicate, phenolic resin, dopamine, tetrabutyl titanate, titanium isopropoxide, zirconium n-butoxide, zirconium sec-butoxide, aluminum isopropoxide or aluminum sec-butoxide.
In one embodiment of the present invention, in step (1), the catalyst is an acidic catalyst or a basic catalyst;
the alkaline catalyst is selected from one or more of sodium hydroxide, potassium hydroxide or concentrated ammonia water;
the acidic catalyst is selected from one or more of acetic acid, formic acid or dilute hydrochloric acid.
In one embodiment of the present invention, in the step (1), the organic solvent is one or more selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, benzene, toluene, diethyl ether, tetrahydrofuran, chloroform or dichloromethane.
In one embodiment of the present invention, in the step (1), the molar ratio of the surfactant, the shell layer precursor, and the catalyst is (0.01 to 1): 1: (0.5-10).
In one embodiment of the present invention, in the step (2), the drying temperature is 30 to 120 ℃ and the drying time is 12 to 120 hours.
In one embodiment of the present invention, in the step (3), the organic alcohol is selected from one or more of ethanol, ethylene glycol, glycerol, n-butanol, isopropanol, n-propanol, n-pentanol or isopentanol;
the magnetic inorganic nano-particle material is selected from ferroferric oxide, gamma-ferric oxide and NiFe2O4、CoFe2O4、CuFe2O4One of nano iron particles, nano nickel or nano cobalt; the size of the magnetic inorganic nano-particles is 10-1000 nm;
the mass percent of the magnetic inorganic nano particles is 0.1-10.0 wt%, the mass percent of the single micelle gel is 0.5-20.0 wt%, and the rest is organic alcohol aqueous solution.
In one embodiment of the invention, in the step (3), the reaction temperature is 30-100 ℃, and the reaction time is 12-96 h; the roasting temperature is 400-1200 ℃, and the roasting time is 2-24 h.
The second purpose of the invention is to provide the magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method of the magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material, the mesoporous shell layer is constructed from the minimum composition unit single micelle of the mesoporous material, the thickness, the aperture, the space group, the composition, the specific surface area and the like of the obtained shell layer can be accurately controlled, and the controllability and the universality are achieved;
(2) the preparation method provided by the invention has simple steps, can directly wrap the mesoporous shell layer on the surface of the magnetic particle, and does not need to additionally introduce an intermediate transition layer;
(3) the magnetic inorganic particle core and ordered mesoporous shell composite material prepared by the invention has sensitive magnetic response characteristic, high specific surface area, large aperture and pore volume, and is expected to be applied to adsorption separation.
Drawings
Fig. 1 is a scanning electron microscope image of the γ -ferric oxide @ mesoporous titanium dioxide core-shell composite material provided in embodiment 1 of the present invention;
FIG. 2 is a drawing of a gamma-ferric oxide @ mesoporous titanium dioxide core-shell composite material according to embodiment 1 of the present invention, with nitrogen being adsorbed and desorbed;
fig. 3 is a pore size distribution diagram of the γ -ferric oxide @ mesoporous titanium dioxide core-shell composite material provided in embodiment 1 of the present invention;
fig. 4 is a magnetic response curve diagram of the γ -ferric oxide @ mesoporous titanium dioxide core-shell composite material provided in embodiment 1 of the present invention;
fig. 5 is a transmission electron microscope image of the γ -ferric oxide @ mesoporous carbon core-shell composite material provided in embodiment 2 of the present invention.
Detailed Description
The invention provides a preparation method of a magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material, which comprises the following steps:
(1) dissolving a surfactant, a shell precursor and a catalyst in an organic solvent to obtain a mixed solution;
(2) drying the mixed solution obtained in the step (1) to obtain single micelle gel;
(3) mixing the single micelle gel obtained in the step (2) with magnetic inorganic nano particles, organic alcohol and water, reacting, washing, drying and roasting a reaction product at a high temperature to obtain the magnetic inorganic nano particle @ ordered mesoporous material core-shell composite material;
wherein the specific surface area of the magnetic inorganic nano-particle @ ordered mesoporous material core-shell composite material is 50-1200m2The mesoporous size is 2-40nm, and the thickness of a mesoporous shell layer is 5-100 nm;
the ordered mesoporous material is selected from one of silicon dioxide, carbon, titanium dioxide, zirconium dioxide or aluminum oxide; the space group of the mesostructure of the ordered mesoporous material is one or a mixture of more of P6mm, Fm3m, Im3m, Pm3n, Fd3m or Ia3 d.
In one embodiment of the present invention, in step (1), the surfactant is selected from one or more of an anionic surfactant, a cationic surfactant or a nonionic surfactant;
the anionic surfactant is selected from one or more of glutamic acid anionic surfactant, alanine anionic surfactant, glycine anionic surfactant or carboxylic acid anionic surfactant;
the cationic surfactant is selected from one or more of alkyl quaternary ammonium salt surfactant, gemini surfactant, meteor hammer surfactant or three-head cationic surfactant;
the nonionic surfactant is selected from one or more of polyethylene oxide-polypropylene oxide, polyethylene oxide-polybutylene oxide, polyethylene oxide-polystyrene or polyethylene oxide-polymethyl methacrylate diblock copolymer, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and polypropylene oxide-polyethylene oxide-polypropylene oxide triblock copolymer.
In one embodiment of the present invention, in the step (1), the shell layer precursor is selected from one of tetraethyl orthosilicate, sodium silicate, tetramethyl orthosilicate, phenolic resin, dopamine, tetrabutyl titanate, titanium isopropoxide, zirconium n-butoxide, zirconium sec-butoxide, aluminum isopropoxide or aluminum sec-butoxide.
In one embodiment of the present invention, in step (1), the catalyst is an acidic catalyst or a basic catalyst;
the alkaline catalyst is selected from one or more of sodium hydroxide, potassium hydroxide or concentrated ammonia water;
the acidic catalyst is selected from one or more of acetic acid, formic acid or dilute hydrochloric acid.
In one embodiment of the present invention, in the step (1), the organic solvent is one or more selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, benzene, toluene, diethyl ether, tetrahydrofuran, chloroform or dichloromethane.
In one embodiment of the present invention, in the step (1), the molar ratio of the surfactant, the shell layer precursor, and the catalyst is (0.01 to 1): 1: (0.5-10).
In one embodiment of the present invention, in the step (2), the drying temperature is 30 to 120 ℃ and the drying time is 12 to 120 hours.
In one embodiment of the present invention, in the step (3), the organic alcohol is selected from one or more of ethanol, ethylene glycol, glycerol, n-butanol, isopropanol, n-propanol, n-pentanol or isopentanol;
the magnetic inorganic nano-particle material is selected from ferroferric oxide, gamma-ferric oxide and NiFe2O4、CoFe2O4、CuFe2O4One of nano iron particles, nano nickel or nano cobalt; the size of the magnetic inorganic nano-particles is 10-1000 nm;
the mass percent of the inorganic magnetic nano particles is 0.1-10.0 wt%, the mass percent of the single micelle gel is 0.5-20.0 wt%, and the balance is organic alcohol aqueous solution.
In one embodiment of the invention, in the step (3), the reaction temperature is 30-100 ℃, and the reaction time is 12-96 h; the roasting temperature is 400-1200 ℃, and the roasting time is 2-24 h.
The invention provides a magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material prepared by the method.
The invention is described in detail below with reference to the figures and specific embodiments.
In the following examples, phenolic resin, gamma-ferric oxide and ferroferric oxide were prepared by the laboratory, and the specific preparation method is described in meng.y.et al, angelw.chem.int.ed.2005, 44,7053; wang.x.et al, j.mater.chem.2004,14,905 and liu.j.et al, angelw.chem.int.ed.2009, 48,5875.
Otherwise, unless otherwise specified, all the conventional commercial raw materials or conventional processing techniques are used in the art.
Example 1
The embodiment provides a gamma-ferric oxide particle @ mesoporous titanium dioxide composite material and a preparation method thereof.
Mixing 0.1mmol of F127 (surfactant), 30mL of tetrahydrofuran and 2.4mmol of concentrated hydrochloric acid (36-38 wt%), stirring at room temperature for 30 minutes to obtain a clear and transparent mixed solution, then adding 1mmol of tetrabutyl titanate, and continuing to stir for one hour; transferring the mixed solution into a constant-temperature drying oven, and standing at 40 ℃ for 48h to obtain white single micelle gel;
dispersing 1.0g of single micelle gel and 100mg of gamma-ferric oxide particles in a mixed solution of 30mL of ethanol and 100mL of water, and then heating at 70 ℃ for 12 h; washing the obtained product with absolute ethyl alcohol, and roasting the washed product for 3h at 500 ℃ in a nitrogen protection atmosphere to remove the surfactant, thereby obtaining the gamma-ferric oxide particle @ mesoporous titanium dioxide composite material.
FIG. 1 is a scanning electron microscope image showing that the gamma-ferric oxide particles @ mesoporous titanium dioxide obtained in example 1 have a regular shape and a uniform size, the size of the pore channel is about 10nm, and the space group is P6 mm.
Fig. 2 is a nitrogen adsorption and desorption isotherm of the γ -ferric oxide particles @ mesoporous titanium dioxide obtained in example 1. The adsorption curve is an IV curve, and a typical mesoporous material adsorption isotherm. Corresponding mesopores are obviously adsorbed at the relative pressure of 0.5-0.8. Specific surface area of the materialIs 128m2/g。
FIG. 3 is a graph showing the pore size distribution of the gamma-ferric oxide particles @ mesoporous titania obtained in example 1. The curves show that the material has a uniform pore size of about 8.0 nm.
FIG. 4 is a magnetic response curve diagram of the gamma-ferric oxide particles @ mesoporous titanium dioxide composite material obtained in example 1, wherein the saturation magnetization of the material is about 75 emu/g.
Example 2
The embodiment provides a gamma-ferric oxide particle @ mesoporous titanium dioxide composite material and a preparation method thereof.
Mixing 0.1mmol of F127 (surfactant), 30mL of tetrahydrofuran and 2.4mmol of concentrated hydrochloric acid (36-38 wt%), stirring at room temperature for 30 minutes to obtain a clear and transparent mixed solution, then adding 1mmol of tetrabutyl titanate, and continuing to stir for one hour; transferring the mixed solution into a constant-temperature drying oven, and standing at 40 ℃ for 48h to obtain white single micelle gel;
dispersing 2.0g of single micelle gel and 100mg of gamma-ferric oxide particles in a mixed solution of 30mL of ethanol and 100mL of water, and then heating at 70 ℃ for 12 h; washing the obtained product with anhydrous ethanol, and roasting at 500 deg.C for 3h under nitrogen protection atmosphere to remove surfactant to obtain a product with shell thickness of 30nm, pore diameter of 8.0nm, and specific surface area of 220m2The composite material is a gamma-ferric oxide particle @ mesoporous titanium dioxide composite material with a space group of P6 mm.
Example 3
The embodiment provides a gamma-ferric oxide particle @ mesoporous titanium dioxide composite material and a preparation method thereof.
Mixing 0.1mmol of F127 (surfactant), 30mL of tetrahydrofuran and 2.4mmol of concentrated hydrochloric acid (36-38 wt%), stirring at room temperature for 30 minutes to obtain a clear and transparent mixed solution, then adding 1mmol of tetrabutyl titanate, and continuing to stir for one hour; transferring the mixed solution into a constant-temperature drying oven, and standing at 40 ℃ for 48h to obtain white single micelle gel;
dispersing 10.0g of single micelle gel and 100mg of gamma-ferric oxide particles in a mixed solution of 30mL of ethanol and 100mL of water, and then heating at 70 ℃ for 12 h;washing the obtained product with anhydrous ethanol, and calcining at 500 deg.C for 3h under nitrogen protection atmosphere to remove surfactant to obtain a shell with thickness of 100nm, pore diameter of 8.0nm, and specific surface area of 500m2The composite material is a gamma-ferric oxide particle @ mesoporous titanium dioxide composite material with a space group of P6 mm.
Example 4
The embodiment provides a gamma-ferric oxide particle @ mesoporous titanium dioxide composite material and a preparation method thereof.
Mixing 0.2mmol of F127 (surfactant), 30mL of tetrahydrofuran and 2.4mmol of concentrated hydrochloric acid (36-38 wt%), stirring at room temperature for 30 minutes to obtain a clear and transparent mixed solution, then adding 1mmol of tetrabutyl titanate, and continuing to stir for one hour; transferring the mixed solution into a constant-temperature drying oven, and standing at 40 ℃ for 48h to obtain white single micelle gel;
dispersing 1.0g of single micelle gel and 100mg of gamma-ferric oxide particles in a mixed solution of 30mL of ethanol and 100mL of water, and then heating at 70 ℃ for 12 h; washing the obtained product with anhydrous ethanol, and roasting at 500 deg.C for 3h under nitrogen protection to remove surfactant to obtain a product with shell thickness of 30nm, pore diameter of 15nm, and specific surface area of 135m2The composite material is characterized by comprising gamma-ferric oxide particles and mesoporous titanium dioxide, wherein the space group of the gamma-ferric oxide particles is Fm3 m.
Example 5
The embodiment provides a gamma-ferric oxide particle @ mesoporous titanium dioxide composite material and a preparation method thereof.
Mixing 0.25mmol of F127 (surfactant), 30mL of tetrahydrofuran and 2.4mmol of concentrated hydrochloric acid (36-38 wt%), stirring at room temperature for 30 minutes to obtain a clear and transparent mixed solution, then adding 1mmol of tetrabutyl titanate, and continuing to stir for one hour; transferring the mixed solution into a constant-temperature drying oven, and standing at 40 ℃ for 48h to obtain white single micelle gel;
dispersing 1.0g of single micelle gel and 100mg of gamma-ferric oxide particles in a mixed solution of 30mL of ethanol and 100mL of water, and then heating at 70 ℃ for 12 h; washing the obtained product with anhydrous ethanol, and roasting at 500 deg.C for 3h under nitrogen protection to remove surfactant to obtain a product with shell thickness of30nm, 20nm of pore diameter and 140m of specific surface area2The composite material is gamma-ferric oxide particles and mesoporous titanium dioxide, and the space group is Im3 m.
Example 6
The embodiment provides a gamma-ferric oxide particle @ mesoporous titanium dioxide composite material and a preparation method thereof.
Mixing 0.5mmol of F127 (surfactant), 30mL of tetrahydrofuran and 2.4mmol of concentrated hydrochloric acid (36-38 wt%), stirring at room temperature for 30 minutes to obtain a clear and transparent mixed solution, then adding 1mmol of tetrabutyl titanate, and continuing to stir for one hour; transferring the mixed solution into a constant-temperature drying oven, and standing at 40 ℃ for 48h to obtain white single micelle gel;
dispersing 1.0g of single micelle gel and 100mg of gamma-ferric oxide particles in a mixed solution of 30mL of ethanol and 100mL of water, and then heating at 70 ℃ for 12 h; washing the obtained product with anhydrous ethanol, and roasting at 500 deg.C for 3h under nitrogen protection to remove surfactant to obtain a product with shell thickness of 30nm, pore diameter of 30nm, and specific surface area of 120m2The composite material is a gamma-ferric oxide particle @ mesoporous titanium dioxide composite material with a space group of Pm3 n.
Example 7
The embodiment provides a gamma-ferric oxide particle @ mesoporous titanium dioxide composite material and a preparation method thereof.
Mixing 1.0mmol of F127 (surfactant), 30mL of tetrahydrofuran and 2.4mmol of concentrated hydrochloric acid (36-38 wt%), stirring at room temperature for 30 minutes to obtain a clear and transparent mixed solution, then adding 1mmol of tetrabutyl titanate, and continuing to stir for one hour; transferring the mixed solution into a constant-temperature drying oven, and standing at 40 ℃ for 48h to obtain white single micelle gel;
dispersing 1.0g of single micelle gel and 100mg of gamma-ferric oxide particles in a mixed solution of 30mL of ethanol and 100mL of water, and then heating at 70 ℃ for 12 h; washing the obtained product with anhydrous ethanol, and roasting at 500 deg.C for 3h under nitrogen protection to remove surfactant to obtain a product with shell thickness of 30nm, pore diameter of 40nm, and specific surface area of 150m2Per g, space group is gamma-ferric oxide particle @ mesoporous titanium dioxide composite material of Ia3dAnd (5) feeding.
Example 8
The embodiment provides a gamma-ferric oxide @ mesoporous carbon core-shell composite material and a preparation method thereof.
Mixing 1mmol of phenol, 1mmol of formaldehyde solution and 10mmol of sodium hydroxide solution to form a clear solution, and reacting at 70 ℃ for 0.5h to obtain the low-molecular-weight phenolic resin prepolymer. Then adding an aqueous solution containing 0.06mmol of F127, uniformly mixing, and drying at 70 ℃ for 24h to obtain a single micelle element.
Dispersing 0.5g of single micelle primitive and 20mg of gamma-ferric oxide in 30mL of water, and then heating at 90 ℃ for 8 h; washing the obtained product with anhydrous ethanol, and calcining at 1200 deg.C for 3h in nitrogen atmosphere to remove surfactant to obtain shell with thickness of 2nm, pore diameter of 5nm, and specific surface area of 1000m2The/g space group is Fd3 m.
Referring to FIG. 5, FIG. 5 shows a transmission electron microscope image showing that the core-shell size of gamma-ferric oxide @ mesoporous carbon is uniform and the shell thickness is about 2 nm.
Example 9
The embodiment provides a ferroferric oxide @ mesoporous aluminum oxide core-shell composite material and a preparation method thereof.
Mixing 0.1mmol of F127, 75mL of tetrahydrofuran and 2.4mmol of concentrated hydrochloric acid (36-38 wt%), stirring at room temperature for 30 minutes to obtain a clear and transparent mixed solution, adding 1mmol of aluminum isopropoxide, and continuing to stir for one hour; transferring the mixed solution into a constant-temperature drying oven, and standing at 40 ℃ for 48h to obtain white single micelle gel;
dispersing 1.0g of single micelle gel and 100mg of ferroferric oxide in a mixed solution of 30mL of ethanol and 100mL of water, and then heating for 24 hours at 70 ℃; washing the obtained product with anhydrous ethanol, and calcining at 700 deg.C for 3h to remove surfactant to obtain a shell with thickness of 10nm, pore diameter of 15nm, and specific surface area of 300m2Per g, the space group is P6mm ferroferric oxide @ mesoporous aluminum oxide core-shell composite material.
Comparative example 1:
compared with the embodiment 1, the comparative example omits the introduction of a surfactant, and the obtained gamma-ferric oxide particle @ mesoporous titanium dioxide composite material cannot form a pore channel.
The above examples and comparative examples are only a few specific cases, but the specific surface area of the core-shell composite material with the magnetic inorganic nanoparticles and the ordered mesoporous material of the present invention can be prepared by the preparation method of the core-shell composite material with the specific surface area of 50-1200m in the following condition ranges2The magnetic inorganic nano-particle @ ordered mesoporous material core-shell composite material has the advantages that the mesoporous size is 2-40nm, the thickness of a mesoporous shell layer is 2-100nm, the space group is one or more of P6mm, Fm3m, Im3m, Pm3n, Fd3m or Ia3 d;
(1) the molar ratio of the surfactant to the shell precursor to the catalyst is (0.01-1): 1: (0.5-10).
(2) The drying temperature is 30-120 ℃, and the drying time is 12-120 h;
(3) the size of the magnetic inorganic nano-particles is 10-1000 nm;
(4) the mass percent of the magnetic inorganic nano particles is 0.1-10.0 wt%, the mass percent of the single micelle gel is 0.5-20.0 wt%, and the rest is organic alcohol aqueous solution;
(5) the reaction temperature is 30-100 ℃, and the reaction time is 12-96 h; the roasting temperature is 400-1200 ℃, and the roasting time is 2-24 h.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material is characterized by comprising the following steps:
(1) dissolving a surfactant, a shell precursor and a catalyst in an organic solvent to obtain a mixed solution;
(2) drying the mixed solution obtained in the step (1) to obtain single micelle gel;
(3) mixing the single micelle gel obtained in the step (2) with magnetic inorganic nano particles, organic alcohol and water, reacting, washing, drying and roasting a reaction product at a high temperature to obtain the magnetic inorganic nano particle @ ordered mesoporous material core-shell composite material;
wherein the specific surface area of the magnetic inorganic nano-particle @ ordered mesoporous material core-shell composite material is 50-1200m2The mesoporous size is 2-40nm, and the thickness of a mesoporous shell layer is 5-100 nm;
the ordered mesoporous material is selected from one of silicon dioxide, carbon, titanium dioxide, zirconium dioxide or aluminum oxide; the space group of the mesostructure of the ordered mesoporous material is one or a mixture of more of P6mm, Fm3m, Im3m, Pm3n, Fd3m or Ia3 d.
2. The preparation method of the magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material as claimed in claim 1, wherein in the step (1), the surfactant is selected from one or more of an anionic surfactant, a cationic surfactant and a nonionic surfactant;
the anionic surfactant is selected from one or more of glutamic acid anionic surfactant, alanine anionic surfactant, glycine anionic surfactant or carboxylic acid anionic surfactant;
the cationic surfactant is selected from one or more of alkyl quaternary ammonium salt surfactant, gemini surfactant, meteor hammer surfactant or three-head cationic surfactant;
the nonionic surfactant is selected from one or more of polyethylene oxide-polypropylene oxide, polyethylene oxide-polybutylene oxide, polyethylene oxide-polystyrene or polyethylene oxide-polymethyl methacrylate diblock copolymer, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer or polypropylene oxide-polyethylene oxide-polypropylene oxide triblock copolymer.
3. The method for preparing the magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material as recited in claim 1, wherein in the step (1), the precursor of the shell layer is selected from one of tetraethyl orthosilicate, sodium silicate, tetramethyl orthosilicate, phenolic resin, dopamine, tetrabutyl titanate, titanium isopropoxide, zirconium n-butoxide, zirconium sec-butoxide, aluminum isopropoxide or aluminum sec-butoxide.
4. The preparation method of the magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material as recited in claim 1, wherein in the step (1), the catalyst is an acidic catalyst or a basic catalyst;
the alkaline catalyst is selected from one or more of sodium hydroxide, potassium hydroxide or concentrated ammonia water;
the acidic catalyst is selected from one or more of acetic acid, formic acid or dilute hydrochloric acid.
5. The preparation method of the magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material as claimed in claim 1, wherein in the step (1), the organic solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, benzene, toluene, diethyl ether, tetrahydrofuran, chloroform or dichloromethane.
6. The preparation method of the magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material as claimed in claim 1, wherein in the step (1), the molar ratio of the surfactant, the shell precursor and the catalyst is (0.01-1): 1: (0.5-10).
7. The preparation method of the magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material as claimed in claim 1, wherein in the step (2), the drying temperature is 30-120 ℃, and the drying time is 12-120 h.
8. The preparation method of the magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material as claimed in claim 1, wherein in the step (3), the organic alcohol is selected from one or more of ethanol, ethylene glycol, glycerol, n-butanol, isopropanol, n-propanol, n-pentanol or isopentanol;
the magnetic inorganic nano-particle material is selected from ferroferric oxide, gamma-ferric oxide and NiFe2O4、CoFe2O4、CuFe2O4One of nano iron particles, nano nickel or nano cobalt; the size of the magnetic inorganic nano-particles is 10-1000 nm;
the mass percent of the magnetic inorganic nano particles is 0.1-10.0 wt%, the mass percent of the single micelle gel is 0.5-20.0 wt%, and the rest is organic alcohol aqueous solution.
9. The preparation method of the magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material as claimed in claim 1, wherein in the step (3), the reaction temperature is 30-100 ℃, and the reaction time is 12-96 hours; the roasting temperature is 400-1200 ℃, and the roasting time is 2-24 h.
10. The magnetic inorganic nanoparticle @ ordered mesoporous material core-shell composite material prepared by the method of any one of claims 1-9.
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