CN102284264B - Method for preparing hydrotalcite coated ferroferric oxide microspheres - Google Patents
Method for preparing hydrotalcite coated ferroferric oxide microspheres Download PDFInfo
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- CN102284264B CN102284264B CN2011101610951A CN201110161095A CN102284264B CN 102284264 B CN102284264 B CN 102284264B CN 2011101610951 A CN2011101610951 A CN 2011101610951A CN 201110161095 A CN201110161095 A CN 201110161095A CN 102284264 B CN102284264 B CN 102284264B
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- ferroferric oxide
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- coated ferroferric
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Abstract
The invention discloses a method for preparing hydrotalcite coated ferroferric oxide core-shell microspheres, and belongs to the field of inorganic nanomaterial synthesis. The method comprises the following steps of: preparing ferroferric oxide microspheres; preparing silica coated ferroferric oxide microspheres; preparing alumina monohydrate sol; impregnating the prepared silica coated ferroferric oxide microspheres into the alumina monohydrate sol for several times to obtain alumina monohydrate and silica coated ferroferric oxide microspheres with a core-shell structure; and putting the obtained composite microspheres into solution containing divalent metal ions, and crystallizing at a certain temperature to obtain the hydrotalcite coated ferroferric oxide core-shell microspheres. By the method, hydrotalcite coated magnetic material core-shell microspheres are prepared for the first time, and the preparation method and application field of a hydrotalcite-like material are expanded due to the introduction of a magnetic core.
Description
Technical field
The invention belongs to the synthetic field of inorganic nano material, particularly a kind of preparation method of hydrotalcite coated ferroferric oxide microballoon.
Background technology
Magnetic material more and more causes the interest that people study because of its advantage of constructing at bioengineering and novel memory device.The bimetallic complex hydroxide is called hydrotalcite (Layered Double Hydroxides again; Be abbreviated as LDHs) be a kind of typical anionic type laminated material; The mutual high degree of dispersion of the hydroxide of divalence and trivalent metal ion and constitute the main body laminate wherein with covalent bond; And be rich in positive charge, interlayer anion ordered arrangement and commutative, laminate metallic element adjustable ratio.In recent years, hydrotalcite-like material since the particular structure characteristics in absorption, catalysis and construct aspect such as functional film and demonstrated very big advantage.Being incorporated into the hydrotalcite laminate to ferric ion obtains magnetic hydrotalcite report has been arranged; The saturation magnetization of the hydrotalcite that this method obtains is lower; Can not well satisfy actual application; And must contain iron ion in this type magnetic hydrotalcite, and the kind of hydrotalcite is comparatively single, and this also is unfavorable for bringing into play the sharpest edges of hydrotalcite.Core-shell type structure with the nano particle of hydrotalcite coated magnetic is constructed with this not only can be brought into play hydrotalcite in many advantages; And can realize the magnetic that material is stronger; This type material is in bio-separation, and targeted drug transportation and Magnetic resonance imaging aspect all have great significance.
Summary of the invention
The objective of the invention is to prepare the microballoon of hydrotalcite coated magnetic nano particle tri-iron tetroxide through the design synthetic route.
Technical scheme of the present invention is the microballoon that at first prepares monohydrate alumina and the common coated ferroferric oxide of silica; Because synthetic hydrotalcite need be at alkaline environment; And silica can decompose under alkaline environment; Utilize this attributes, the tri-iron tetroxide microballoon of monohydrate alumina and silica parcel has promptly obtained monodispersed hydrotalcite coated ferroferric oxide microballoon through growth in situ under alkaline environment.
The preparation process of hydrotalcite coated ferroferric oxide microballoon of the present invention is following:
1). the preparation of tri-iron tetroxide microballoon:
Ferric trichloride and the 7-8g sodium acetate of 2-3g are added in the ethylene glycol of 90-100ml, stir the back at 180-220 ℃ of following crystallization 6-12 hour, use the absolute ethyl alcohol centrifuge washing, 50-80 ℃ dry 6-12 hour, obtain finely dispersed tri-iron tetroxide microballoon;
2). the preparation of silica coated ferroferric oxide microballoon:
0.05-0.1g tri-iron tetroxide powder is added to contains the 80-100ml absolute ethyl alcohol; 10-20ml deionized water and 5-10ml mass concentration are in the there-necked flask of 20-30% ammoniacal liquor; And then add the 0.3-0.4ml ethyl orthosilicate, stirring at room 4-6 hour, adopt the absolute ethyl alcohol centrifuge washing to neutral; 50-80 ℃ dry 6-12 hour, obtain finely dispersed silica coated ferroferric oxide microballoon;
3). the silica coated ferroferric oxide microballoon of monohydrate alumina parcel:
A, the 10-12g aluminium isopropoxide is dissolved in the 80-100ml deionized water; 85-90 ℃ was stirred 20-30 minute down; Regulate pH value to 3-4 with the nitric acid of 0.5-1mol/L, continue to stir 2-3 hour, obtained the monohydrate alumina powder to bone dry in room temperature held 4-7 days then; Getting dried monohydrate alumina powder 5-6g and be added in the 100-110ml deionized water, was 85-90 ℃ stirred 1-2 hour down, adds 9-10ml? 0.5-1mol/L nitric acid continue to stir that cool to room temperature promptly obtains monohydrate alumina colloidal sol after 6-7 hour;
B, get step 2) in the silica coated ferroferric oxide microballoon 0.05-0.1g that obtains be put in the monohydrate alumina colloidal sol that obtains among the 20-30ml step a and stirred 1-2 hour; Centrifuge washing then; Repeat to add and stir centrifuge washing after 1-2 hour in the monohydrate alumina colloidal sol that obtains among the 20-30ml step a; Repeat to obtain after 6-10 time the silica coated ferroferric oxide microballoon of monohydrate alumina parcel, monohydrate alumina is an outermost layer;
4). the preparation of hydrotalcite coated ferroferric oxide microballoon:
A, preparation 70-100ml concentration are the divalent metal nitrate solution of 0.05-0.1mol/L, add 0.1-0.2g ammonium nitrate then, use mass concentration to regulate pH value to 8-9 as the ammoniacal liquor of 1-2%;
B, the silica coated ferroferric oxide microballoon of getting the monohydrate alumina parcel of 0.05-0.1g step 3) preparation are added in the solution in the steps A; 80-100 ℃ was reacted 12-36 hour; Reacted product is used the absolute ethyl alcohol centrifuge washing, and 60-70 ℃ obtained hydrotalcite coated ferroferric oxide microballoon in dry 6-12 hour.
Described divalent metal nitrate is selected from Mg (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Ca (NO
3)
2, Cu (NO
3)
2, Fe (NO
3)
2, Mn (NO
3)
2In a kind of.
The present invention has realized the preparation of the core-shell type microballoon of hydrotalcite coated magnetic material first, and the magnetic ferroferric oxide microballoon of hydrotalcite parcel not only can be brought into play the advantage of hydrotalcite self, and this Nano microsphere has stronger magnetic simultaneously.This material is in bio-separation, and targeted drug transportation and Magnetic resonance imaging aspect all have great significance, and have widened the application of hydrotalcite.
Description of drawings
Fig. 1 is the stereoscan photograph that the embodiment of the invention 1 obtains hydrotalcite coated ferroferric oxide microballoon.
Fig. 2 is the transmission electron microscope photo that the embodiment of the invention 1 obtains hydrotalcite coated ferroferric oxide microballoon.
Fig. 3 is the XRD spectra that the embodiment of the invention 1 obtains hydrotalcite coated ferroferric oxide microballoon; Abscissa is 2 θ, unit: degree; Ordinate is an intensity.
The specific embodiment
Embodiment 1
1). the preparation of tri-iron tetroxide microballoon:
The ferric trichloride of 2.7g and the sodium acetate of 7.2g are added in the ethylene glycol of 100ml, and the back that stirs is 200 ℃ of following crystallization 8 hours, and with absolute ethyl alcohol centrifuge washing six times, 60 ℃ of dryings 12 hours obtain finely dispersed tri-iron tetroxide microballoon;
2). the preparation of silica coated ferroferric oxide microballoon:
The tri-iron tetroxide powder of 0.1g is added to the absolute ethyl alcohol that contains 80ml; The deionized water of 20ml and 10ml mass concentration are in the there-necked flask of 25% ammoniacal liquor; And then the ethyl orthosilicate of adding 0.32ml, stirring at room 6 hours adopts the absolute ethyl alcohol centrifuge washing to neutral; 60 ℃ of dryings 12 hours obtain finely dispersed silica coated ferroferric oxide microballoon;
3). the silica coated ferroferric oxide microballoon of monohydrate alumina parcel:
A, the aluminium isopropoxide of 11.8g is dissolved in the deionized water of 100ml, 85 ℃ were stirred 20 minutes down, regulated pH value to 3 with the nitric acid of 1mol/L, continued stirring 2 hours, were placed on following 5 days of room temperature then to bone dry; Get dried monohydrate alumina powder 5.8g and be added in the deionized water of 107ml, 85 ℃ were stirred 1 hour down, and the nitric acid that adds 9.5ml 1mol/L continues to stir that cool to room temperature promptly obtains a water alumina sol after 6 hours;
B, get step 2) in the tri-iron tetroxide microballoon 0.1g of the silica parcel that obtains be put in the monohydrate alumina colloidal sol that obtains among the 30mla and stirred 1 hour; Centrifuge washing then; Repeat to add and stir centrifuge washing after 1 hour in the monohydrate alumina colloidal sol that obtains among the 30ml step a; Repeat to obtain after 8 times the silica coated ferroferric oxide microballoon of monohydrate alumina parcel, monohydrate alumina is an outermost layer;
4). the preparation of hydrotalcite coated ferroferric oxide microballoon:
A, preparation 100ml concentration are the Ni (NO of 0.1mol/L
3)
2Solution adds 48 gram ammonium nitrate then, and the use mass concentration is 1% ammoniacal liquor adjusting pH value to 6.5;
B, the silica coated ferroferric oxide microballoon of getting the monohydrate alumina parcel of 0.05g step 3) preparation are added in the solution in the steps A; 80 ℃ were reacted 36 hours; Reacted product is used the absolute ethyl alcohol centrifuge washing, and 60 ℃ of dryings obtained the tri-iron tetroxide microballoon of hydrotalcite parcel in 12 hours.
Embodiment 2
1). the preparation of tri-iron tetroxide microballoon:
The ferric trichloride of 2.5g and the sodium acetate of 7.0g are added in the ethylene glycol of 90ml, and the back that stirs is 180 ℃ of following crystallization 10 hours, and with absolute ethyl alcohol centrifuge washing six times, 50 ℃ of dryings 10 hours obtain finely dispersed tri-iron tetroxide microballoon;
2). the preparation of silica coated ferroferric oxide microballoon:
The tri-iron tetroxide powder of 0.05g is added to the absolute ethyl alcohol that contains 100ml; The deionized water of 15ml and 8ml mass concentration are in the there-necked flask of 20% ammoniacal liquor; And then the ethyl orthosilicate of adding 0.35ml, stirring at room 5 hours adopts the absolute ethyl alcohol centrifuge washing to neutral; 50 ℃ of dryings 10 hours obtain finely dispersed silica coated ferroferric oxide microballoon;
3). the silica coated ferroferric oxide microballoon of monohydrate alumina parcel:
A, the aluminium isopropoxide of 11g is dissolved in the deionized water of 80ml, 90 ℃ were stirred 30 minutes down, regulated pH value to 4 with the nitric acid of 0.5mol/L, continued stirring 3 hours, were placed on following 7 days of room temperature then to bone dry; Get dried monohydrate alumina powder 5g and be added in the deionized water of 90ml, 80 ℃ were stirred 2 hours down, and the nitric acid that adds 9ml 1mol/L continues to stir that cool to room temperature promptly obtains a water alumina sol after 7 hours;
B, get step 2) in the tri-iron tetroxide microballoon 0.05g of the silica parcel that obtains be put in the monohydrate alumina colloidal sol that obtains among the 20ml a and stirred 2 hours; Centrifuge washing then; Repeat to add and stir centrifuge washing after 2 hours in the monohydrate alumina colloidal sol that obtains among the 20ml step a; Repeat to obtain after 6 times the silica coated ferroferric oxide microballoon of monohydrate alumina parcel, monohydrate alumina is an outermost layer;
4). the preparation of hydrotalcite coated ferroferric oxide microballoon:
A, preparation 80ml concentration are the Ni (NO of 0.05mol/L
3)
2Solution adds 0.15 gram ammonium nitrate then, and the use mass concentration is 2% ammoniacal liquor adjusting pH value to 8;
B, the silica coated ferroferric oxide microballoon of getting the monohydrate alumina parcel of 0.1g step 3) preparation are added in the solution in the steps A; 85 ℃ were reacted 24 hours; Reacted product is used the absolute ethyl alcohol centrifuge washing, and 50 ℃ of dryings obtained the tri-iron tetroxide microballoon of hydrotalcite parcel in 10 hours.
Claims (1)
1. the preparation method of a hydrotalcite coated ferroferric oxide microballoon is characterized in that, its concrete operations step is following:
1). the preparation of tri-iron tetroxide microballoon:
Ferric trichloride and the 7-8g sodium acetate of 2-3g are added in the ethylene glycol of 90-100mL, stir the back at 180-220 ℃ of following crystallization 6-12 hour, use the absolute ethyl alcohol centrifuge washing, 50-80 ℃ dry 6-12 hour, obtain finely dispersed tri-iron tetroxide microballoon;
2). the preparation of silica coated ferroferric oxide microballoon:
0.05-0.1g tri-iron tetroxide powder is added to contains the 80-100mL absolute ethyl alcohol; 10-20mL deionized water and 5-10mL mass concentration are in the there-necked flask of 20-30% ammoniacal liquor; And then add the 0.3-0.4mL ethyl orthosilicate, stirring at room 4-6 hour, adopt the absolute ethyl alcohol centrifuge washing to neutral; 50-80 ℃ dry 6-12 hour, obtain finely dispersed silica coated ferroferric oxide microballoon;
3). the silica coated ferroferric oxide microballoon of monohydrate alumina parcel:
A, the 10-12g aluminium isopropoxide is dissolved in the 80-100mL deionized water; 85-90 ℃ was stirred 20-30 minute down;, continue to stir 2-3 hour to 3-4 with the nitre acid for adjusting pH value of 0.5-1mol/L, obtained the monohydrate alumina powder to bone dry in room temperature held 4-7 days then; Get dried monohydrate alumina powder 5-6g and be added in the 100-110mL deionized water, 85-90 ℃ was stirred 1-2 hour down, and the nitric acid that adds 9-10mL 0.5-1mol/L continues to stir that cool to room temperature promptly obtains monohydrate alumina colloidal sol after 6-7 hour;
B, get step 2) in the silica coated ferroferric oxide microballoon 0.05-0.1g that obtains be put in the monohydrate alumina colloidal sol that obtains among the 20-30mL step a and stirred 1-2 hour; Centrifuge washing then; Repeat to add the monohydrate alumina colloidal sol that obtains among the 20-30mL step a; Stir centrifuge washing after 1-2 hour, repeat to obtain after 6-10 time the silica coated ferroferric oxide microballoon of monohydrate alumina parcel, monohydrate alumina is an outermost layer;
4). the preparation of hydrotalcite coated ferroferric oxide microballoon:
A, preparation 70-100mL concentration are the divalent metal nitrate solution of 0.05-0.1mol/L, add 0.1-0.2g ammonium nitrate then, use mass concentration to regulate the pH value to 8-9 as the ammoniacal liquor of 1-2%;
B, the silica coated ferroferric oxide microballoon of getting the monohydrate alumina parcel of 0.05-0.1g step 3) preparation are added in the solution in the steps A; 80-100 ℃ was reacted 12-36 hour; Reacted product is used the absolute ethyl alcohol centrifuge washing, and 60-70 ℃ obtained hydrotalcite coated ferroferric oxide microballoon in dry 6-12 hour;
Described divalent metal nitrate is selected from Mg (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Ca (NO
3)
2, Cu (NO
3)
2, Fe (NO
3)
2, Mn (NO
3)
2In a kind of.
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| CN103127886A (en) * | 2013-03-05 | 2013-06-05 | 南京大学 | Hollow magnetic meso pore SiO2 nano-material and preparation method |
| CN104900419B (en) * | 2015-04-16 | 2017-06-30 | 电子科技大学 | Use CNTs@SiO2@Ni/Al LDH core shell structures are the ultracapacitor of positive electrode |
| CN105289434B (en) * | 2015-12-08 | 2018-01-26 | 河南大学 | A kind of Fe3O4The preparation method and applications of@CA β CD nanoparticles |
| CN106475134B (en) * | 2016-09-22 | 2019-05-17 | 华东师范大学 | A kind of hydrotalcite is the nucleocapsid catalyst and its preparation and application that shell/molecular sieve is core |
| CN107297195B (en) * | 2017-08-18 | 2020-12-08 | 江苏海普功能材料有限公司 | Magnetic defluorinating agent and preparation method thereof |
| CN109054744B (en) * | 2018-07-16 | 2020-10-02 | 太原理工大学 | Method for preparing magnetic abrasive particles by sol-gel method |
| CN109225220B (en) * | 2018-08-28 | 2020-11-20 | 北京化工大学 | Roasted hydrotalcite catalyst with magnetic core, preparation and application in toluene side chain formaldehyde alkylation reaction |
| CN115652650A (en) * | 2022-10-22 | 2023-01-31 | 贵州省材料产业技术研究院 | Flexible electromagnetic shielding PVC composite film and preparation method thereof |
| CN116371352A (en) * | 2023-03-31 | 2023-07-04 | 北京化工大学 | Calcium-containing hydrotalcite-vermiculite composite material and preparation method and application thereof |
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| CN100382890C (en) * | 2005-12-06 | 2008-04-23 | 北京化工大学 | Aluminium-based pseudo-hydrotalcite structuralization catalyst, and its prepn. method |
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