CN111747451A - Ferroferric oxide/mesoporous silica magnetic composite particle and super-assembly method thereof - Google Patents
Ferroferric oxide/mesoporous silica magnetic composite particle and super-assembly method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 51
- 239000011246 composite particle Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- BRXOKRLIIVYICJ-UHFFFAOYSA-N butoxy(trihydroxy)silane Chemical compound CCCCO[Si](O)(O)O BRXOKRLIIVYICJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007865 diluting Methods 0.000 claims abstract description 3
- 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 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 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 6
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention provides a super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles, belonging to the field of nano composite materials. The invention comprises the following steps: dissolving a nano silicon bottle in triethylene glycol, adding iron acetylacetonate to obtain a mixed solution, cooling the mixed solution to room temperature, diluting, centrifuging, taking a solid, washing and drying to obtain a ferroferric oxide/asymmetric nano silicon bottle; the ferroferric oxide/asymmetric nano silicon bottle, triethanolamine and hexadecyl trimethyl ammonium chloride solution are dissolved in water, normal hexane solution containing n-butyl orthosilicate is added, centrifugation is carried out, solid is taken, washing, drying and calcining are carried out, and the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle is obtained.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a super-assembly method of ferroferric oxide/mesoporous silica magnetic composite particles.
Background
At present, the method for preparing the ferroferric oxide/asymmetric mesoporous silica magnetic composite particles generally comprises the steps of firstly preparing magnetic ferroferric oxide particles or clusters with different sizes as an inner core by a solvothermal method or a solvent alternation method and the like, and then coating a silica layer on the outer surface of the magnetic ferroferric oxide particles or clusters. The composite nano particles prepared by the method are generally in core-shell structures, and the loaded substances are limited by the mesoporous layer and cannot be loaded with a large amount of substances or large-volume substances. For example, patent CN 104069513 a utilizes a solvent alternation method to prepare hollow silica submicron spheres with ferroferric oxide particles and silica cores, but the hollow spheres are difficult to be used as containers because the hollow cavities of the materials cannot be used; in patent CN 110451581A, ferroferric oxide particles are synthesized by a hydrothermal method, and an improved stober method is further utilized to prepare the double-layer ferroferric oxide @ silicon dioxide magnetic composite nano-particles, so that the material has the defects of poor dispersibility, incapability of loading and the like. The invention adds the magnetic ferroferric oxide layer and the mesoporous silicon layer on the basis of the nano silicon bottle by the super-assembly method, well keeps the cavity inside the nano silicon bottle, and the mesoporous silicon layers are arranged inside and outside the nano silicon bottle, so that the specific surface area is greatly increased, and a good space is provided for loading various substances.
Disclosure of Invention
The invention aims to solve the problem of the deficiency of ferroferric oxide and silicon dioxide composite materials in the prior art, and aims to provide a super-assembly method for preparing ferroferric oxide/asymmetric mesoporous silicon dioxide composite particles.
The invention provides a super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles, which can also have the following characteristics: the method comprises the following steps:
dissolving a nano silicon bottle in triethylene glycol, adding iron acetylacetonate to obtain a mixed solution, heating the mixed solution to react at the temperature of 250-300 ℃ under the protection of inert gas, cooling to room temperature, diluting, centrifuging, taking a solid, washing and drying to obtain a ferroferric oxide/asymmetric nano silicon bottle;
and step two, dissolving the ferroferric oxide/asymmetric nano silicon bottle, triethanolamine and a hexadecyl trimethyl ammonium chloride solution in water, adding an n-hexane solution containing n-butyl silicate, reacting at 50-80 ℃, centrifuging, taking a solid, washing, drying and calcining to obtain the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle.
The super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle provided by the invention can also have the following characteristics: the preparation method of the nano silicon bottle comprises the following steps:
dissolving polyvinylpyrrolidone in n-amyl alcohol, adding ethanol, an ammonia water solution of sodium citrate, n-butyl silicate and 3-chloropropyltriethoxysilane, standing, centrifuging, taking a solid, washing and drying to obtain the nano silicon bottle.
The super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle provided by the invention can also have the following characteristics: wherein, the molar concentration of the polyvinylpyrrolidone is 0.01mol/L-0.02mol/L, and the volume ratio of the n-amyl alcohol, the ethanol, the ammonia water solution of the sodium citrate, the n-butyl silicate and the 3-chloropropyltriethoxysilane is 1 (0.08-0.1), 0.42-0.63, 0.1-0.2 and 0.01-0.02.
The super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle provided by the invention can also have the following characteristics: wherein the concentration of the ammonia water solution of the sodium citrate is 0.02-0.03 mol/L.
The super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle provided by the invention can also have the following characteristics: wherein the average size of the nano silicon bottle is 200nm-300 nm.
The super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle provided by the invention can also have the following characteristics: wherein the mass ratio of the nano silicon bottle to the ferric acetylacetonate is (20-50): (80-120).
The super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle provided by the invention can also have the following characteristics: wherein, in the step one, the heating rate is 3 ℃/min.
The super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle provided by the invention can also have the following characteristics: wherein the mass ratio of the ferroferric oxide/asymmetric nano silicon bottle to the triethanolamine is (0.02-0.03): (0.08-0.10); the volume ratio of the hexadecyl trimethyl ammonium chloride solution to the normal hexane to the n-butyl orthosilicate is (10-15): (3-5): (0.04-0.07).
The super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle provided by the invention can also have the following characteristics: wherein in the second step, the heating rate is 2-4 ℃/min.
The ferroferric oxide/asymmetric mesoporous silica magnetic composite particle provided by the invention has the characteristics that the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle is prepared by the super-assembly method of any ferroferric oxide/asymmetric mesoporous silica magnetic composite particle.
The invention discloses a super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles, which comprises the following specific principles: synthesizing flask-shaped nano-silica by a water-in-oil microemulsion template method, thermally decomposing ferric acetylacetonate in situ on the basis of the flask-shaped nano-silica, uniformly generating ferroferric oxide nano-particles on the inner and outer surfaces of a nano-silica bottle, and finally generating a uniform mesoporous silica layer on the ferroferric oxide surface by a bidirectional interface method.
Action and Effect of the invention
According to the super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particles, the magnetic ferroferric oxide layer and the mesoporous silicon layer are added on the basis of the nano silicon bottle, and the cavity in the nano silicon bottle is well reserved, so that the specific surface area is greatly increased, and meanwhile, a good space is provided for loading various substances.
Drawings
FIG. 1(a-d) is a TEM image of a nano-silica bottle, ferroferric oxide/asymmetric mesoporous silica magnetic composite particle and their magnifications in step one to step three of example 1 of the present invention;
FIG. 2 is an XRD spectrum of a ferroferric oxide/asymmetric nano-silicon bottle in step two of example 1 of the invention;
FIG. 3 is a nitrogen adsorption/desorption curve of the mesoporous Si layer in step III of example 1 of the present invention;
fig. 4 is a size curve of mesopores of the mesoporous silicon layer in step three of example 1 of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is specifically described below by combining the embodiment and the attached drawings.
< example 1>
Super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles
The method comprises the following steps: dissolving 1.0g of polyvinylpyrrolidone into 10mL of n-amyl alcohol, adding 1.0mL of ethanol after complete dissolution, fully mixing, adding 420 mu L of ammonia water solution dissolved with 0.02mol/L of sodium citrate into the solution, violently shaking for 10min, adding 100 mu L of n-butyl silicate and 10 mu L of 3-chloropropyltriethoxysilane, continuing shaking for 2min, standing at room temperature for 5h, centrifuging to obtain a precipitate, cleaning with a mixed solution of deionized water and ethanol, and drying to obtain a nano silicon bottle;
step two: weighing 20mg of the nano silicon bottle obtained in the step one, dispersing the nano silicon bottle in 20mL of triethylene glycol, performing ultrasonic treatment to completely dissolve the nano silicon bottle, adding 80mg of ferric acetylacetonate under magnetic stirring, and performing nitrogen protection on the mixed solution at the temperature of 3 ℃ for min-1Heating the mixture to 278 ℃ at the heating rate, reacting for 30min to generate a ferroferric oxide/asymmetric nano silicon bottle, cooling to room temperature after the reaction is finished, adding 20mL of ethanol diluted solution, centrifuging, washing with ethanol, and drying under vacuum;
step three: and (3) dissolving 25mg of ferroferric oxide/asymmetric nano silicon bottle, 0.09g of triethanolamine and 12mL of 25% 25 wt% hexadecyl trimethyl ammonium chloride aqueous solution in 18mL of deionized water, stirring at 60 ℃ for 1h, adding 4mL of n-hexane solution containing 40 mu L of n-butyl orthosilicate, reacting at 60 ℃ for 8h, centrifugally collecting a product, washing with ethanol to remove residual reactants, placing the dried powder in a tubular furnace, and calcining at 500 ℃ for 4h to obtain the brown yellow ferroferric oxide/asymmetric mesoporous silicon dioxide magnetic composite particle.
< example 2>
A super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles comprises the following steps: dissolving 1.5g of polyvinylpyrrolidone into 10mL of n-amyl alcohol, adding 1.0mL of ethanol after complete dissolution, fully mixing, adding 570 mu L of ammonia water solution dissolved with 0.03mol/L of sodium citrate into the solution, violently shaking for 10min, adding 200 mu L of n-butyl silicate and 20 mu L of 3-chloropropyltriethoxysilane, continuing shaking for 2min, standing at room temperature for 3h, centrifuging to obtain a product, cleaning by using a mixed solution of deionized water and ethanol, and drying to obtain a nano silicon bottle;
step two: weighing 20mg of the nano silicon bottle obtained in the step one, dispersing the nano silicon bottle in 20mL of triethylene glycol, performing ultrasonic treatment to completely dissolve the nano silicon bottle, adding 80mg of ferric acetylacetonate under magnetic stirring, and performing nitrogen protection on the mixed solution at the temperature of 3 ℃ for min-1Heating the mixture to 278 ℃ at the heating rate, reacting for 30min to generate a ferroferric oxide/asymmetric nano silicon bottle, cooling to room temperature after the reaction is finished, adding 20mL of ethanol diluted solution, centrifuging, washing with ethanol, and drying under vacuum;
step three: and (3) dissolving 25mg of ferroferric oxide/asymmetric nano silicon bottle, 0.09g of triethanolamine and 12mL of 25% 25 wt% hexadecyl trimethyl ammonium chloride aqueous solution in 18mL of deionized water, stirring at 60 ℃ for 1h, adding 4mL of n-hexane solution containing 40 mu L of n-butyl orthosilicate, reacting at 60 ℃ for 8h, centrifugally collecting a product, washing with ethanol to remove residual reactants, placing the dried powder in a tubular furnace, and calcining at 500 ℃ for 4h to obtain the brown yellow ferroferric oxide/asymmetric mesoporous silicon dioxide magnetic composite particle.
< example 3>
Super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles
The method comprises the following steps: dissolving 1.5g of polyvinylpyrrolidone into 10mL of n-amyl alcohol, adding 1.0mL of ethanol after complete dissolution, fully mixing, adding 570 mu L of ammonia water solution dissolved with 0.03mol/L of sodium citrate into the solution, violently shaking for 10min, adding 200 mu L of n-butyl silicate and 20 mu L of 3-chloropropyltriethoxysilane, continuing shaking for 2min, standing at room temperature for 3h, centrifuging to obtain a product, cleaning by using a mixed solution of deionized water and ethanol, and drying to obtain a nano silicon bottle;
step two: weighing 50mg of the nano silicon bottle obtained in the step one, dispersing the nano silicon bottle in 20mL of triethylene glycol, performing ultrasonic treatment to completely dissolve the nano silicon bottle, adding 120mg of ferric acetylacetonate under magnetic stirring, and performing nitrogen protection on the mixed solution at the temperature of 3 ℃ for min-1Heating the mixture to 278 ℃ at the heating rate, reacting for 30min to generate a ferroferric oxide/asymmetric nano silicon bottle, cooling to room temperature after the reaction is finished, adding 20mL of ethanol diluted solution, centrifuging, washing with ethanol, and drying under vacuum;
step three: and (3) dissolving 25mg of ferroferric oxide/asymmetric nano silicon bottle, 0.09g of triethanolamine and 12mL of 25% 25 wt% hexadecyl trimethyl ammonium chloride aqueous solution in 18mL of deionized water, stirring at 60 ℃ for 1h, adding 4mL of n-hexane solution containing 70 mu L of n-butyl orthosilicate, reacting at 60 ℃ for 8h, centrifugally collecting a product, washing with ethanol to remove residual reactants, placing the dried powder in a tubular furnace, and calcining at 550 ℃ for 5h to obtain the brown yellow ferroferric oxide/asymmetric mesoporous silicon dioxide magnetic composite particle.
Effects and effects of the embodiments
According to the super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particles, the magnetic ferroferric oxide layer and the mesoporous silicon layer are added on the basis of the nano silicon bottle, so that the cavity inside the nano silicon bottle is well reserved; because the mesoporous silicon layers are arranged inside and outside the nano silicon bottle, the specific surface area is greatly increased, and a good space is provided for loading various substances.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. A super-assembly method of ferroferric oxide/mesoporous silica magnetic composite particles is characterized by comprising the following steps:
dissolving a nano silicon bottle in triethylene glycol, adding iron acetylacetonate to obtain a mixed solution, heating the mixed solution to react at the temperature of 250-300 ℃ under the protection of inert gas, cooling to room temperature, diluting, centrifuging, taking a solid, washing and drying to obtain a ferroferric oxide/asymmetric nano silicon bottle;
and step two, dissolving the ferroferric oxide/asymmetric nano silicon bottle, triethanolamine and a hexadecyl trimethyl ammonium chloride solution in water, adding an n-hexane solution containing n-butyl silicate, reacting at 50-80 ℃, centrifuging, taking a solid, washing, drying and calcining to obtain the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle.
2. The super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles according to claim 1, characterized in that:
wherein, the preparation of the nano silicon bottle comprises the following steps:
dissolving polyvinylpyrrolidone in n-amyl alcohol, adding ethanol, an ammonia water solution of sodium citrate, n-butyl silicate and 3-chloropropyltriethoxysilane, standing, centrifuging, taking a solid, washing and drying to obtain the nano silicon bottle.
3. The super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles according to claim 2, characterized in that:
wherein the molar concentration of the polyvinylpyrrolidone is 0.01-0.02 mol/L, and the volume ratio of the n-amyl alcohol, the ethanol, the ammonia water solution of the sodium citrate, the n-butyl orthosilicate and the 3-chloropropyltriethoxysilane is 1 (0.08-0.1), 0.42-0.63, (0.1-0.2) and 0.01-0.02.
4. The super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles according to claim 2, characterized in that:
wherein the concentration of the ammonia water solution of the sodium citrate is 0.02-0.03 mol/L.
5. The super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles according to claim 2, characterized in that:
wherein the average size of the nano silicon bottle is 200nm-300 nm.
6. The super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles according to claim 1, characterized in that:
wherein the mass ratio of the nano silicon bottle to the ferric acetylacetonate is (20-50): (80-120).
7. The super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles according to claim 1, characterized in that:
wherein, in the step one, the heating rate is 3 ℃/min.
8. The super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles according to claim 1, characterized in that:
wherein the mass ratio of the ferroferric oxide/asymmetric nano silicon bottle to the triethanolamine is (0.02-0.03): (0.08-0.10); the volume ratio of the hexadecyl trimethyl ammonium chloride solution to the n-hexane to the n-butyl orthosilicate is (10-15): (3-5): (0.04-0.07).
9. The super-assembly method of ferroferric oxide/asymmetric mesoporous silica magnetic composite particles according to claim 1, characterized in that:
wherein in the second step, the heating rate of calcination is 2-4 ℃/min.
10. A ferroferric oxide/asymmetric mesoporous silica magnetic composite particle, characterized in that the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle is prepared by the super-assembly method of the ferroferric oxide/asymmetric mesoporous silica magnetic composite particle according to any one of claims 1 to 9.
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| CN112972677A (en) * | 2021-02-22 | 2021-06-18 | 上海交通大学医学院附属第九人民医院 | Porous magnetic diagnosis and treatment agent, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN101623653A (en) * | 2008-07-10 | 2010-01-13 | 中国石油化工股份有限公司 | Method for modifying titanium-silicon molecular sieve material |
| CN106517216A (en) * | 2016-11-03 | 2017-03-22 | 北京化工大学 | Biodegradable mesoporous carbon and silicon nano-sphere and method for preparing same |
| CN108404891A (en) * | 2018-01-31 | 2018-08-17 | 江苏大学 | Magnetic molecularly imprinted adsorbent of a kind of hollow single hole of Ianus type and preparation method thereof |
| CN110357169A (en) * | 2019-07-31 | 2019-10-22 | 蚌埠学院 | A kind of preparation method of the magnetic mesoporous silica composite nanoparticle of yolk-eggshell structure |
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| JPH07138023A (en) * | 1993-09-21 | 1995-05-30 | Kawasaki Steel Corp | Magnetite particle and its production |
| CN101623653A (en) * | 2008-07-10 | 2010-01-13 | 中国石油化工股份有限公司 | Method for modifying titanium-silicon molecular sieve material |
| CN106517216A (en) * | 2016-11-03 | 2017-03-22 | 北京化工大学 | Biodegradable mesoporous carbon and silicon nano-sphere and method for preparing same |
| CN108404891A (en) * | 2018-01-31 | 2018-08-17 | 江苏大学 | Magnetic molecularly imprinted adsorbent of a kind of hollow single hole of Ianus type and preparation method thereof |
| CN110357169A (en) * | 2019-07-31 | 2019-10-22 | 蚌埠学院 | A kind of preparation method of the magnetic mesoporous silica composite nanoparticle of yolk-eggshell structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112972677A (en) * | 2021-02-22 | 2021-06-18 | 上海交通大学医学院附属第九人民医院 | Porous magnetic diagnosis and treatment agent, preparation method and application |
| CN112972677B (en) * | 2021-02-22 | 2023-08-25 | 上海交通大学医学院附属第九人民医院 | Porous magnetic diagnosis and treatment agent, preparation method and application |
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