CN107507690A - A kind of core shell structure Fe3O4@SiO2Nano magnetic composite materials synthetic method - Google Patents

A kind of core shell structure Fe3O4@SiO2Nano magnetic composite materials synthetic method Download PDF

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CN107507690A
CN107507690A CN201710875704.7A CN201710875704A CN107507690A CN 107507690 A CN107507690 A CN 107507690A CN 201710875704 A CN201710875704 A CN 201710875704A CN 107507690 A CN107507690 A CN 107507690A
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sio
magnetic composite
composite materials
nano
shell structure
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CN107507690B (en
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冯国栋
苗康康
罗小林
潘哲
裴霏
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Baoji University of Arts and Sciences
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Baoji University of Arts and Sciences
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/36—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets

Abstract

The invention discloses a kind of core shell structure Fe3O4@SiO2Nano magnetic composite materials synthetic method.This method first obtains Fe3O4The alcoholic solution of nano-powder, then according to Fe under neutral environment3O4It is (1.5 4) with tetraethyl orthosilicate mass ratio:1 ratio, 5 15h are reacted at 100 150 DEG C in homogeneous reactor, obtain nanometer Fe3O4@SiO2Nano magnetic composite materials.The inventive method is carried out under neutral environment, does not add other materials, course of reaction green is pollution-free；The Fe being prepared3O4@SiO2Nano magnetic composite materials have core shell structure, and SiO2Thickness degree between 4 20nm, concentrate by distribution；Fe simultaneously3O4@SiO2Nano magnetic composite materials have individual particle, good dispersion and good magnetic response feature；Tetraethyl orthosilicate dosage is few compared with conventional method, and its utilization rate is higher.

Description

A kind of core shell structure Fe3O4@SiO2Nano magnetic composite materials synthetic method
Technical field
The invention belongs to magnetic composite preparation field, and in particular to a kind of Fe3O4@SiO2Nano magnetic composite materials Synthetic method.
Background technology
With the fast development of nano material, nanometer Fe3O4@SiO2Magnetic composite microsphere is as a kind of important function material Material, it is widely used in being catalyzed, adsorbs, that the separation of target medicine carrier, cell, nuclear magnetic resonance, immunoassay, nucleic acid hybridize etc. is numerous Field.
At present, Fe3O4@SiO2The preparation of magnetic composite is largely reported.Such as patent CN 201110361859.1 disclose a kind of Fe3O4@SiO2Composite material and preparation method thereof, this method is with tetraethyl orthosilicate：Fe3O4Weight Amount is than being 1：(0.064~0.64), Fe is prepared under the reaction condition of concentrated hydrochloric acid and ammoniacal liquor3O4@SiO2.Such as paper again JCS.2017,139,4954-4961, CHEM ENG J.327 (2017) 648-655,《The micro-nano functional material of magnetic it is controllable Prepare and its removal to water pollutant is studied》(Shao Yanming, Lanzhou University, 2016), patent CN106277066, CN104475012, CN201710079429, CN201410784808.3 and CN201410147748.4 disclose specific preparation Fe3O4@SiO2Composite process, summarize the above method and find：On the one hand, above-mentioned synthesis Fe3O4@SiO2Reaction be in alkali Carried out in property environment, follow-up waste liquid need to be handled, cause cost increase, and easily cause environmental pollution；On the other hand, on State tetraethyl orthosilicate in method (TEOS) and Fe3O4Weight than scope 1：(0.17~0.54), therefore form Nano-meter SiO_22Shell It is more that layer consumes TEOS raw materials, the defects of TEOS utilization rates are relatively low be present.
So far, there is not yet anacidity, alkali-free, it is salt-free, additive-free under the conditions of, while obtain core using a small amount of TEOS Shell structure Fe3O4@SiO2The synthetic method report of magnetic composite.
The content of the invention
The purpose of the present invention is to be directed to existing preparation Fe3O4@SiO2The defects of magnetic composite method is present, there is provided one Kind is under neutral environment, and the core shell structure Fe that TEOS utilization rates are high3O4@SiO2Nano magnetic composite materials synthetic method.
In order to realize the purpose of the present invention, the present inventor is finally obtained as follows by lot of experiments research and unremitting effort Technical scheme：A kind of core shell structure Fe3O4@SiO2Nano magnetic composite materials synthetic method, comprises the following steps：
Step 1：By Fe3O4Nano-powder is dissolved in alcoholic solution, is well mixed, is obtained Fe3O4Alcoholic solution；
Step 2：The Fe obtained to step 13O4Alcoholic solution adds tetraethyl orthosilicate, Fe3O4With the mass ratio of tetraethyl orthosilicate For (1.5-4)：1, it is well mixed, 5-15h is reacted at 100-150 DEG C in homogeneous reactor, by cooling, Magneto separate, washing With nanometer Fe is obtained after drying3O4@SiO2Magnetic composite.
It is further preferred that core shell structure Fe of the present invention3O4@SiO2Nano magnetic composite materials synthetic method, in step 1 The Fe3O4Nano-powder grain diameter is 20-65nm.
It is further preferred that core shell structure Fe of the present invention3O4@SiO2Nano magnetic composite materials synthetic method, wherein step Described in 2 reaction be anacidity, alkali-free, it is salt-free, additive-free under the conditions of carry out.
It is further preferred that core shell structure Fe of the present invention3O4@SiO2Nano magnetic composite materials synthetic method, wherein step Fe described in 23O4Mass ratio with the tetraethyl orthosilicate is (1.8-3.6):1.
It is further preferred that core shell structure Fe of the present invention3O4@SiO2Nano magnetic composite materials synthetic method, in step 2 The reaction is to be carried out under stirring condition in homogeneous reactor, and the speed of agitator is 10-50r/min.
It is further preferred that core shell structure Fe of the present invention3O4@SiO2Nano magnetic composite materials synthetic method, in step 2 The reaction temperature is 100-140 DEG C, reacts 5-10h.
It is further preferred that core shell structure Fe of the present invention3O4@SiO2Nano magnetic composite materials synthetic method, in step 1 The alcoholic solution is ethanol solution, the Fe3O4The mass ratio of nano-powder and the ethanol solution is 1：(200-1000).
It is further preferred that core shell structure Fe of the present invention3O4@SiO2Nano magnetic composite materials synthetic method, the ethanol Concentration of polymer solution is 20-80%.
It is further preferred that core shell structure Fe of the present invention3O4@SiO2Nano magnetic composite materials synthetic method, wherein step Speed of agitator is 10-40r/min in 2.
The present invention has the following technical effect that relative to prior art：
(1) reaction is carried out under neutral environment, does not add other materials, course of reaction green is pollution-free；
(2) Fe being prepared3O4@SiO2Nano magnetic composite materials have nucleocapsid structure, and SiO2Thickness degree is in 4- Between 20nm, distribution is concentrated；
(3) Fe being prepared3O4@SiO2There is nano magnetic composite materials individual particle, good dispersion and good magnetic to ring Answer feature；
(4) Fe is prepared3O4@SiO2Tetraethyl orthosilicate dosage is few compared with conventional method during nano magnetic composite materials, its utilization rate It is higher.
Brief description of the drawings
Fig. 1 is Fe in the embodiment of the present invention 23O4Nano-powder SEM schemes；
Fig. 2 is Fe in the embodiment of the present invention 23O4Nano-powder XRD；
Fig. 3 is the Fe that the embodiment of the present invention 2 obtains3O4@SiO2Nano magnetic composite materials SEM schemes；
Fig. 4 is the Fe that the embodiment of the present invention 2 obtains3O4@SiO2Nano magnetic composite materials XRD；
Fig. 5 is Fe in the embodiment of the present invention 23O4Nano-powder TEM schemes；
Fig. 6 is Fe in the embodiment of the present invention 23O4@SiO2Nano magnetic composite materials TEM schemes；
Fig. 7 is the Fe that the embodiment of the present invention 2 obtains3O4@SiO2The magnetic response of nano magnetic composite materials；
Fig. 8 is the material TEM figures obtained in comparative example 1 under the conditions of 65 DEG C；
Fig. 9 is the material SEM figures and partial enlargement TEM figures that comparative example 2 obtains；
Figure 10 is the material SEM figures and partial enlargement TEM figures that comparative example 3 obtains.
Embodiment
The embodiment of the present invention is described further below, wherein, Fe used in the embodiment of the present invention3O4 Nano-powder can be prepared according to existing open method, particle size range 20-65nm.
Embodiment 1
Fe3O4@SiO2It is prepared by nano magnetic composite materials：
Step 1：By Fe3O4Nano-powder is added in ptfe autoclave, wherein Fe3O4The average grain of nano-powder Footpath is 35nm, adds the ethanol-water solution that ethanol mass concentration is 80%, Fe3O4The weight of nano-powder and ethanol-water solution Than for 1：1000, ultrasonic disperse 15min, obtain Fe3O4Ethanol solution；
Step 2：To Fe3O4Ethanol solution in add tetraethyl orthosilicate, TEOS and Fe3O4Weight ratio be 1：1.8, surpass Sound disperses 15min, encapsulates ptfe autoclave, is put into homogeneous reactor, rotating speed 10r/min is controlled, in 100 DEG C of temperature Lower reaction 10h, cooling, Magneto separate, is washed with water, and dries, obtains nanometer Fe3O4@SiO2Magnetic composite.
Microexamination discovery, SiO are carried out to product2Shell thickness is homogeneous, average thickness 12nm.
Embodiment 2
Fe3O4@SiO2It is prepared by nano magnetic composite materials：
Step 1：By Fe3O4Nano-powder is added in ptfe autoclave, as Fig. 1,2,5 show the present embodiment Fe used3O4Nano-powder, its average grain diameter are 65nm, add the ethanol-water solution that ethanol mass concentration is 20%, Fe3O4Receive The weight of ground rice body and ethanol-water solution ratio is 1：200, ultrasonic disperse 30min, obtain Fe3O4Ethanol solution；
Step 2：To Fe3O4Ethanol solution in add tetraethyl orthosilicate, TEOS and Fe3O4Weight ratio be 1：3.6, surpass Sound disperses 30min, encapsulates ptfe autoclave, is put into homogeneous reactor, rotating speed 40r/min is controlled, in 140 DEG C of temperature Lower reaction 5h, cooling, Magneto separate, is washed with water, and dries, obtains nanometer Fe3O4@SiO2Magnetic composite.
As shown in Fig. 3,4,6, SiO is shown2Load to Fe3O4And be nucleocapsid structure, it has been observed that SiO2Shell thickness is equal One, average thickness 4nm.
To the nanometer Fe being prepared3O4@SiO2Magnetic composite carries out magnetic effect experiment, as described in Figure 7, at several points Microsphere sample has moved into magnet on one side in clock, and solution reaches macroscopic clear, illustrates that magnetic composite microsphere has letter Just, quick Magneto separate characteristic.
Embodiment 3
Fe3O4@SiO2It is prepared by nano magnetic composite materials：
Step 1：By Fe3O4Nano-powder is added in ptfe autoclave, wherein Fe3O4The average grain of nano-powder Footpath is 60nm, adds the ethanol-water solution that ethanol mass concentration is 50%, Fe3O4The weight of nano-powder and ethanol-water solution Than for 1：500, ultrasonic disperse 20min, obtain Fe3O4Ethanol solution；
Step 2：To Fe3O4Ethanol solution in add tetraethyl orthosilicate, TEOS and Fe3O4Weight ratio be 1：2.4, surpass Sound disperses 20min, encapsulates ptfe autoclave, is put into homogeneous reactor, rotating speed 25r/min is controlled, in 120 DEG C of temperature Lower reaction 8h, cooling, Magneto separate, is washed with water, and dries, obtains nanometer Fe3O4@SiO2Magnetic composite.
Microexamination discovery, SiO are carried out to product2Shell thickness is homogeneous, average thickness 12nm.
Embodiment 4
Fe3O4@SiO2It is prepared by nano magnetic composite materials：
Step 1：By Fe3O4Nano-powder is added in ptfe autoclave, wherein Fe3O4The average grain of nano-powder Footpath is 40nm, adds the ethanol-water solution that ethanol mass concentration is 60%, Fe3O4The weight of nano-powder and ethanol-water solution Than for 1：750, ultrasonic disperse 25min, obtain Fe3O4Ethanol solution；
Step 2：To Fe3O4Ethanol solution in add tetraethyl orthosilicate, TEOS and Fe3O4Weight ratio be 1：3.0, surpass Sound disperses 25min, encapsulates ptfe autoclave, is put into homogeneous reactor, rotating speed 30r/min is controlled, in 110 DEG C of temperature Lower reaction 9h, cooling, Magneto separate, is washed with water, and dries, obtains nanometer Fe3O4@SiO2Magnetic composite.
Microexamination discovery, SiO are carried out to product2Shell thickness is homogeneous, average thickness 10nm.
Comparative example 1
Processing procedure and parameter are same as Example 2, respectively in rate-determining steps 2 reaction temperature be 50 DEG C, 65 DEG C, 80 DEG C, 95℃、110℃、125℃、140℃、155℃。
Microexamination is carried out to product, found when reaction temperature is respectively 50 DEG C, 65 DEG C, 80 DEG C, 95 DEG C, 155 DEG C.When, Product structure all such as Fig. 8 reaction products at 65 DEG C are similar, Fe3O4Nano grain surface does not form SiO2Clad, and in temperature Spend for 110 DEG C, 125 DEG C, 140 DEG C when, product be core shell structure Fe3O4@SiO2, and SiO2The thickness of shell is between 8-20nm.
Comparative example 2
Processing procedure and parameter are same as Example 2, and difference is dripped before ptfe autoclave is encapsulated in step 2 It is 9.5 to add alkali lye regulation mixed solution pH, and reaction carries out microexamination after terminating to product, as shown in figure 9, remaining as Fe3O4Receive Ground rice body, and SiO is not formed on its surface2Clad.Illustrate, cannot be such as the embodiment of the present application 2 under alkaline reaction environment Shown Core-shell structure material.
Comparative example 3
Processing procedure and parameter are identical with the embodiment of the present invention 2, and difference is to encapsulate polytetrafluoroethylene (PTFE) in step 2 anti- After answering kettle, it is put into air dry oven and is reacted, reaction carries out microexamination discovery after terminating to product, as shown in Figure 10, Material surface does not form SiO2Clad.The comparative example is combined with embodiment 2, illustrates that homogeneous reactor is forming core shell structure Course of reaction in play irreplaceable effect.

Claims (8)

  1. A kind of 1. core shell structure Fe3O4@SiO2Nano magnetic composite materials synthetic method, it is characterised in that comprise the following steps：
    Step 1：By Fe3O4Nano-powder is dissolved in alcoholic solution, is well mixed, is obtained Fe3O4Alcoholic solution；
    Step 2：The Fe obtained to step 13O4Alcoholic solution adds tetraethyl orthosilicate, Fe3O4Mass ratio with tetraethyl orthosilicate is (1.5-4):1, be well mixed, react 5-15h at 100-150 DEG C in homogeneous reactor, by cooling, Magneto separate, washing and Nanometer Fe is obtained after drying3O4@SiO2Magnetic composite.
  2. 2. core shell structure Fe according to claim 13O4@SiO2Nano magnetic composite materials synthetic method, it is characterised in that： Fe described in step 13O4Nano-powder grain diameter is 20-65nm.
  3. 3. core shell structure Fe according to claim 13O4@SiO2Nano magnetic composite materials synthetic method, it is characterised in that： Described in step 2 reaction be anacidity, alkali-free, it is salt-free, additive-free under the conditions of carry out.
  4. 4. core shell structure Fe according to claim 13O4@SiO2Nano magnetic composite materials synthetic method, it is characterised in that： Wherein Fe in step 23O4Mass ratio with tetraethyl orthosilicate is (1.8-3.6):1.
  5. 5. core shell structure Fe according to claim 13O4@SiO2Nano magnetic composite materials synthetic method, it is characterised in that： Reaction is to be carried out under stirring condition in homogeneous reactor described in step 2, and the speed of agitator is 10-40r/min.
  6. 6. core shell structure Fe according to claim 13O4@SiO2Nano magnetic composite materials synthetic method, it is characterised in that： Reaction temperature described in step 2 is 100-140 DEG C, reacts 5-10h.
  7. 7. core shell structure Fe according to claim 13O4@SiO2Nano magnetic composite materials synthetic method, it is characterised in that： Alcoholic solution described in step 1 is ethanol solution, the Fe3O4The mass ratio of nano-powder and the ethanol solution is 1：(200- 1000)。
  8. 8. core shell structure Fe according to claim 73O4@SiO2Nano magnetic composite materials synthetic method, it is characterised in that： Described ethanol solution mass concentration is 20-80%.
CN201710875704.7A 2017-09-25 2017-09-25 A kind of core-shell structure Fe3O4@SiO2Nano magnetic composite materials synthetic method Expired - Fee Related CN107507690B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111085183A (en) * 2018-10-24 2020-05-01 中国石油化工股份有限公司 Silicon oxide and titanium oxide composite material and synthesis method thereof

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