CN101625919B - Preparation method of meso-porous nanometer magnetic material - Google Patents
Preparation method of meso-porous nanometer magnetic material Download PDFInfo
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- CN101625919B CN101625919B CN200910098273A CN200910098273A CN101625919B CN 101625919 B CN101625919 B CN 101625919B CN 200910098273 A CN200910098273 A CN 200910098273A CN 200910098273 A CN200910098273 A CN 200910098273A CN 101625919 B CN101625919 B CN 101625919B
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Abstract
The invention relates to a preparation method of a meso-porous nanometer magnetic material. The preparation method is characterized by comprising the following steps: (1) adopting a sol-gel compounding hydrothermal method to directly compound a meso-porous material containing a nanometer magnetic material in a framework; dissolving a certain amount of block copolymer or surface active agent to an acidic/alkaline aqueous solution; uniformly stirring at a constant temperature; then dripping a certain amount of ethyl orthosilicate and adding a certain amount of various dissoluble salts of iron, cobalt, nickel, and the like; continuing to stir at the temperature for 10-30 hours; adjusting a pH value before hydrothermal treatment at 100 DEG C for 1-3 days; filtering products; washing ethanol twice; drying at 60-80 DEG C; and calcining at 550-750 DEG C in air for 6-10 hours to obtain the meso-porous nanometer magnetic material containing the nanometer magnetic material in the framework. The over-long one-dimensional nanometer material synthesized by the method has a favorable microstructure and can promote the application of the one-dimensional nanometer material to the aspects of integrated circuits and functional element devices, such as nanometer electronic and photoelectronic devices, and the like.
Description
Technical field
The invention belongs to the inorganic nano material preparation process technology field, be specifically related to a kind of preparation method of meso-porous nanometer magnetic material of new structure.
Background technology
At present, nano magnetic material has potential application prospect in fields such as harmless magnetic seal, superelevation magnetic recording, biological medicine and wideband suction ripples.At biomedicine field, nano magnetic material has represented huge advantage in directions such as biological magnetic separation, target medicine carrier, the controls of tumour magnetic thermotherapy.Nano magnetic material can directly make medicine reach diseased organ through the mode of external magnetic field effect or injection as pharmaceutical carrier, forms accumulation and discharges medicine at this organ under the outside magnetic field effect, reaches the purpose of curing the disease.Compare with conventional method, have following advantage as pharmaceutical carrier with nano magnetic material: be prone to reach diseased organ, target property high, be prone to absorb, drug side-effect is little, drug effect is high.The research that with the nano magnetic material is pharmaceutical carrier has at present become hot research fields such as inorganic nano chemistry, life science.According to scholarly forecast, utilize meso-porous nanometer magnetic material as pharmaceutical carrier, rely on magnetic thermotherapy and medicine acting in conjunction to be expected to capture persistent ailments such as cancer.
Ordered mesoporous silica dioxide has suitable mesoporous aperture, huge specific area, the pore passage structure of rule, adjustable mesoporous aperture and excellent physical and chemical stability, is considered to a milestone in the synthetic field of inorganic material.Utilize Metaporous silicon dioxide material assemble nanometer particle, not only can avoid the agglomeration traits of nano material, also can guarantee to produce coupling between the nano material and between nano material and the mesoporous wall, represent characteristics such as the light that makes new advances, electricity, magnetic.The biological stability of earth silicon material is higher; And the chemical synthesis process of meso-porous nanometer magnetic material is simple; Mesoporous material has the incomparable structural advantage of other medicines carrier again simultaneously: the ordered mesoporous pore canals structure; Not only can carry more medicine, and help the release of medicine.Require at room temperature to have stronger magnetic for this type pharmaceutical carrier, guarantee that pharmaceutical carrier has response faster in magnetic field to external world, make medicine have more target property, more be prone at lesion locations accumulation and release medicine.
Mesoporous material is mainly being used main employing shell structurre aspect the drug targeting transmission at present; With mesoporous material magnetic material is wrapped in core position; The research in this respect of unit such as Shanghai Inst. of Silicate, Chinese Academy of Sciences, Shanghai Communications University is in international prostatitis [W.Zhao; Et al.J.Am.Chem.Soc., 127 (2005) 8916; S.M.Zhu, et al.Micropor.Mesopor.Mater., 106 (2007) 56].Mesoporous microsphere preparation of drug carriers method is complicated, and adopting this structure mainly is that the magnetic property of nano magnetic material of core position is bigger as pharmaceutical carrier, thereby makes medicine in the process of transmission, have more target property, more easy to control.And less about the research report of mesoporous silicon dioxide nano magnetic material, and mainly concentrate on γ-Fe both at home and abroad
2O
3, Fe
3O
4, Co
3O
4The meso-porous nanometer magnetic material of doping/filling [E.Kockrick, et al.Adv.Mater., 19 (2007) 3021; J.-S.Jung, et al.J.Magn.Magn.Mater., 272-276 (2004) e 1157; T.Tajiri, et al.J.Phys.Soc.Jpn., 75 (2006) 113704; S.V.Kolotilov, et al.J.Solid State Chem., 179 (2006) 2426]; But relevant report shows that the magnetic of meso-porous nanometer magnetic material is not strong; Even superparamagnetism [E.Delahaye, et al.J.Phys.Chem.B, 110 (2006) 26001] appears.Said material magnetic responsiveness to external world is slow or do not have response, is not suitable for the carrier as targeted drug.
The micro-structural control aspect of meso-porous nanometer magnetic material also has a lot of work to remain to be carried out in a deep going way, can further strengthen the magnetic of meso-porous nanometer magnetic material.If directly the stronger Metaporous silicon dioxide material of synthesizing magnetic can guarantee that not only mesoporous material has magnetic response characteristic preferably and adsorptivity, also can go up largely and simplify preparation technology.
Summary of the invention
The meso-porous nanometer magnetic material that the objective of the invention is synthetic a kind of new structure; On mesoporous wall and the duct in introduce respectively nanometer soft/retentive material; Rely on the coupling between the nano material; Promote the magnetic property of meso-porous nanometer magnetic material, the nano magnetic material of preparation can be widely used in fields such as biological magnetic separation, targeted drug transmission and magnetic recording.
To achieve these goals, the technical scheme of the present invention's employing is following:
A kind of preparation method of meso-porous nanometer magnetic material of new structure, it is by following steps:
1, adopt collosol and gel to combine to contain in the directly synthetic skeleton of hydro thermal method the mesoporous material of nano magnetic material: with a certain amount of block polymer or surfactant (P123; F127, CTAB etc.) be dissolved in acid or the alkaline aqueous solution, constant temperature stirs at a certain temperature; Drip a certain amount of tetraethoxysilane (TEOS) then; And add salt such as a certain amount of various soluble iron, cobalt, nickel, and continue stir about 10～30h under this temperature, regulate pH value afterwards 100 ℃ of hydro-thermals 1～3 day; Product is filtered; After twice, 60～80 ℃ of oven dry of washing with alcohol in air 550～750 ℃ of calcining 6～10h, obtain containing in the skeleton mesoporous nano magnetic material of nano magnetic material.
2, utilize infusion process in the mesoporous material duct, to introduce nano magnetic material: to choose in water-soluble or other solvent of all kinds of salt of mesoporous nano magnetic material, solubility of a certain amount of step 1 gained, stir.60～80 times dryings, obtain the mesoporous nano material of new structure at last at 550～750 ℃ of calcining 6～10h after after the solvent evaporated residue being cleaned three times.
The preparation method of the meso-porous nanometer magnetic material of above-mentioned a kind of new structure is characterized in that described mesoporous material comprises the design of ordered mesoporous material (MCM series, SBA is serial, FDU is serial, KIT series etc.) and unordered mesoporous material; Its composition comprises all kinds of mesoporous simple substance/compound-materials such as silicon dioxide, carbon, carborundum and oxide.
The preparation method of the meso-porous nanometer magnetic material of above-mentioned a kind of new structure is characterized in that the nano magnetic material in the described mesoporous framework is simple substance or alloyed oxide magnetic materials such as iron, cobalt, nickel; Nano magnetic material is nano particle or nano wire in its duct.
The preparation method of the meso-porous nanometer magnetic material of above-mentioned a kind of new structure is characterized in that the nano magnetic material in the described mesopore orbit is simple substance/alloy magnetic materials such as iron, cobalt, nickel; Also can be each quasi-metal oxides such as iron, cobalt, nickel, ferrite (Conjugate ferrite, barium ferrite, strontium ferrite, nickel-zinc ferrite, violent Zn ferrite etc.) magnetic material; And all kinds of magnetic compound magnetic materials.
The mesoporous magnetic material technology of the nucleocapsid structure that method provided by the invention is more traditional is simple, and less demanding to experimental facilities, cost is low; In order to improve the magnetic property of mesoporous nano magnetic material, adopt the mesoporous nano magnetic material of hydro thermal method and infusion process synthesizing new structure; The mesoporous nano magnetic material of the inventive method preparation has good magnetic performance and thermal stability preferably, can be widely used in that biological magnetic separates, fields such as targeted drug transmission and magnetic recording.
Description of drawings
Fig. 1 is the meso-porous nanometer magnetic material structural representation;
Fig. 2 is little angle XRD;
Fig. 3 is the XRD curve;
Fig. 4 is the VSM curve.
Specific embodiments
Below in conjunction with embodiment the present invention is described further, but the scope of application of the present invention does not receive the restriction of these embodiment.
As shown in Figure 1, on mesoporous wall and the duct in introduce respectively nanometer soft/retentive material.
Embodiment 1:
With 2g block polymer (P123 (EO)
20(PO)
70(EO)
20) be dissolved in HCl and the 10ml H of 50ml 2M
2Among the O, stir 3h at 39 ℃ of constant temperature; Drip the tetraethoxysilane (TEOS) of 2.5ml then, gluey suspension-turbid liquid can appear in stir about 30min, and regulates pH value between 7～8 with ammoniacal liquor; Add an amount of ferric nitrate (Fe (NO)
39H
2O) aqueous solution makes that the iron and the ratio of the molecular number of silicon are 15: 100, continues to stir 24h down at 39 ℃; Solution is transferred in the stainless steel hydro-thermal still of polytetrafluoroethylene, and at 100 ℃ of hydro-thermal 72h; Question response finishes, and at 750 ℃ of calcining 6h, removes template after 60 ℃ of oven dry.After fully grinding, obtain the SBA-15 mesopore molecular sieve of skeleton iron content 150 ℃ of dry a couple of days.
Get the above-mentioned SBA-15 of the obtaining mesopore molecular sieve of 1g and be dissolved in about 20ml absolute ethyl alcohol, 5mmol cobalt acetate (Co (CH
3COO)
24H
2O) at 50 ℃ of slow solvent flashings, residue cleaned three times after 80 ℃ dry 24 hours down, obtained Co in 6 hours 550 ℃ of calcinings at last
3O
4/ Fe
2O
3-SBA-15 nano magnetic material.Wherein accompanying drawing 2,3,4 provides the Co of preparation respectively
3O
4/ Fe
2O
3Little angle XRD, XRD and the VSM curve of-SBA-15.
Embodiment 2:
2.5g CTAB is dissolved in the 60g water, adds the 20ml concentrated ammonia liquor, stirring at room drips 14mlTEOS for a moment, adds an amount of ferric nitrate (Fe (NO)
39H
2O) aqueous solution makes that the iron and the ratio of the molecular number of silicon are 3: 100, and solution continue is stirred 2-3h, and 100 ℃ of hydro-thermals are 3 days then.Product is filtered, washing, drying, template is gone out in 550 ℃ of roastings.
Get the above-mentioned MCM-41 of the obtaining mesopore molecular sieve of 1g and be dissolved in about 20ml absolute ethyl alcohol, 2.5mmol cobalt nitrate (Co (NO)
26H
2O) and 5mmol ferric nitrate (Fe (NO)
39H
2O) at 50 ℃ of slow solvent flashings, residue cleaned three times after 80 ℃ dry 24 hours down, obtained CoFe in 6 hours 550 ℃ of calcinings at last
2O
4/ Fe
2O
3-MCM-41 nano magnetic material.
Embodiment 3:
4.11g CTAB is dissolved in the 21g water, adds 0.38g NaOH, stirring at room a moment, Dropwise 5 mlTEOS continues solution to stir 2-3h, adds an amount of cobalt nitrate (Co (NO)
26H
2O) aqueous solution makes that the iron and the ratio of the molecular number of silicon are 10: 100, the back 100 ℃ of hydro-thermals that stir 3 days.Product is filtered, washing, drying, template is gone out in 550 ℃ of roastings.
Get the above-mentioned MCM-48 of the obtaining mesopore molecular sieve of 1g and be dissolved in the anhydrous water of about 20ml, 0.1mmol barium nitrate (Ba (NO)
2) and 1.2mmol ferric nitrate (Fe (NO)
39H
2O) at 40 ℃ of slow solvent flashings, residue cleaned three times after 80 ℃ dry 24 hours down, obtained BaFe in 6 hours 550 ℃ of calcinings at last
12O
19/ Co
3O
4-MCM-48 nano magnetic material.
Embodiment 4:
Block polymer (F127 (EO) with 8g
106(PO)
70(EO)
106) be dissolved in 5M HCl water (40ml) solution, stir 3h at 40 ℃ of following constant temperature, drip the tetraethoxysilane (TEOS) of 25ml then, add an amount of ferric nitrate (Fe (NO)
39H
2O) aqueous solution makes that the iron and the ratio of the molecular number of silicon are 6: 100, continues stir about 20h under this temperature, and question response finishes, product is filtered, after twice, 60 ℃ of oven dry of washing with alcohol in air 550 ℃ of calcining 6h, remove template.
Get the above-mentioned SBA-16 of the obtaining mesopore molecular sieve of 1g and be dissolved in the anhydrous water of about 20ml, 0.1mmol barium nitrate (Ba (NO)
2) and 1.2mmol ferric nitrate (Fe (NO)
39H
2O) at 40 ℃ of slow solvent flashings, residue cleaned three times after 80 ℃ dry 24 hours down, obtained BaFe in 6 hours 550 ℃ of calcinings at last
12O
19/ Fe
2O
3-SBA-16 nano magnetic material.
Claims (2)
1. the preparation method of a meso-porous nanometer magnetic material, it is characterized in that: the preparation method has the following steps:
1) adopt collosol and gel to combine to contain in the directly synthetic skeleton of hydro thermal method the mesoporous material of nano magnetic material: 2.5g CTAB is dissolved in the 60g water, adds the 20ml concentrated ammonia liquor, stirring at room drips 14mlTEOS for a moment, adds an amount of ferric nitrate Fe (NO
3)
39H
2The O aqueous solution makes that the iron and the ratio of the molecular number of silicon are 3: 100, and solution continue is stirred 2-3h, and 100 ℃ of hydro-thermals are 3 days then, product is filtered, and washing, drying, template is removed in 550 ℃ of roastings;
2) utilize infusion process in the mesoporous material duct, to introduce nano magnetic material: to get the 1g above-mentioned steps and obtain the MCM-41 mesopore molecular sieve and be dissolved in the 20ml absolute ethyl alcohol, 2.5mmol cobalt nitrate Co (NO
3)
26H
2O and 5mmol ferric nitrate Fe (NO
3)
39H
2O is at 50 ℃ of slow solvent flashings, residue is cleaned three times after 80 ℃ dry 24 hours down, obtained CoFe in 6 hours 550 ℃ of calcinings at last
2O
4/ Fe
2O
3-MCM-41 meso-porous nanometer magnetic material.
2. the preparation method of a meso-porous nanometer magnetic material, it is characterized in that: the preparation method has the following steps:
1) adopt collosol and gel to combine to contain in the directly synthetic skeleton of hydro thermal method the mesoporous material of nano magnetic material: with 2g block polymer P123 (EO)
20(PO)
70(EO)
20Be dissolved in HCl and the 10mlH of 50ml 2M
2Among the O, stir 3h, drip the tetraethoxysilane TEOS of 2.5ml then, stir 30min, gluey suspension-turbid liquid can occur, and regulate pH value between 7～8 with ammoniacal liquor at 39 ℃ of constant temperature; Add an amount of ferric nitrate Fe (NO
3)
39H
2The O aqueous solution makes that the iron and the ratio of the molecular number of silicon are 15: 100, continues to stir 24h down at 39 ℃; Solution is transferred in the stainless steel hydro-thermal still of polytetrafluoroethylene, and at 100 ℃ of hydro-thermal 72h; Question response finishes, and at 750 ℃ of calcining 6h, removes template after 60 ℃ of oven dry, after fully grinding, obtains the SBA-15 mesopore molecular sieve of skeleton iron content 150 ℃ of dry a couple of days;
2) utilize infusion process in the mesoporous material duct, to introduce nano magnetic material: to get the above-mentioned SBA-15 of the obtaining mesopore molecular sieve of 1g and be dissolved in the 20ml absolute ethyl alcohol, 5mmol cobalt acetate Co (CH
3COO)
24H
2O is at 50 ℃ of slow solvent flashings, residue is cleaned three times after 80 ℃ dry 24 hours down, obtained Co in 6 hours 550 ℃ of calcinings at last
3O
4/ Fe
2O
3-SBA-15 meso-porous nanometer magnetic material.
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| US8425651B2 (en) * | 2010-07-30 | 2013-04-23 | Baker Hughes Incorporated | Nanomatrix metal composite |
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| CN103638988B (en) * | 2013-12-06 | 2015-06-17 | 上海师范大学 | Magnetic mesoporous material, and preparation method and application of magnetic mesoporous material |
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| CN104353416A (en) * | 2014-11-07 | 2015-02-18 | 南京理工大学 | Magnetic ordered mesopore composite material, as well as preparation and application thereof |
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| CN106006661A (en) * | 2016-05-03 | 2016-10-12 | 陕西理工学院 | Preparation method of magnetic SBA-15 mesoporous molecular sieve |
| CN106865627B (en) * | 2017-02-28 | 2018-12-07 | 四川理工学院 | Ultra-thin Ni-Co layer structure hydroxide and its preparation method and application |
| CN108821349A (en) * | 2018-06-29 | 2018-11-16 | 国网湖南省电力有限公司 | The hydrothermal synthesis method of distributed generation resource energy storage material cobaltosic oxide thin spherical joint |
| CN112374878B (en) * | 2020-10-29 | 2021-07-27 | 武汉理工大学 | Barium ferrite ceramic material and preparation method thereof |
| CN113921261B (en) * | 2021-08-12 | 2023-10-20 | 中国计量大学 | Preparation method of high-performance high-resistivity composite magnet |
| CN116422335A (en) * | 2023-03-28 | 2023-07-14 | 浙江大学 | Mesoporous metal oxide catalyst and preparation method and application thereof |
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