CN107362775A - A kind of core-shell structure magnetic fibre shape nano SiO 2 particle and its preparation method and application - Google Patents

A kind of core-shell structure magnetic fibre shape nano SiO 2 particle and its preparation method and application Download PDF

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CN107362775A
CN107362775A CN201710581115.8A CN201710581115A CN107362775A CN 107362775 A CN107362775 A CN 107362775A CN 201710581115 A CN201710581115 A CN 201710581115A CN 107362775 A CN107362775 A CN 107362775A
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hfe
sio
core
shell structure
fibre shape
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牛建瑞
李宗泽
李文亚
李再兴
刘艳芳
贾秀秀
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Hebei University of Science and Technology
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    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

A kind of core-shell structure magnetic fibre shape nano SiO 2 particle and its preparation method and application, it is related to a kind of preparation method of core-shell structure magnetic fibre shape silica.Its kernel is hollow ferroso-ferric oxide, and outer layer is fibrous silica.The present invention prepares hollow ferroferric oxide nano granules by solvent-thermal method, then obtains the hollow ferroferric oxide nano granules for wrapping up fibrous silica of core-shell structure after preparing presoma calcining by sol-gal process.The high saturation magnetic intensity that has of the magnetic fibre shape nano SiO 2 particle of the present invention is 23 ~ 30emu/g, and big specific surface area is 200 ~ 400m2/ g, big pore volume and aperture are respectively 0.5 ~ 0.8cm3/ g and 8 ~ 20nm.Obtained nano particle is used for the Adsorption to persistent organic pollutants such as dyestuffs in water, has good effect, and can quickly be separated by externally-applied magnetic field from solution.

Description

A kind of core-shell structure magnetic fibre shape nano SiO 2 particle and preparation method thereof and Using
Technical field
The present invention relates to a kind of core-shell structure magnetic fibre shape nano SiO 2 particle, preparation method and applications, category In technical field of nanometer material preparation.
Background technology
Removal for hardly degraded organic substance in waste water, absorption method is one of important method, compared with other method, absorption Method species is various, easy to operate, technology mature.Absorption method goes hardly degraded organic substance in water removal mainly to pass through solid absorbent Physics and chemisorbed performance, organic matter is enriched with reach into adsorbent remove or reduce Organic substance in water process.Inhale The key of attached method is the suitable adsorbent of selection, and many materials such as silica, zeolite, activated carbon, resin etc. are applied to inhale Attached dose.But these adsorbents have cost higher, the shortcomings of being not easy to be desorbed.Along with the development of nano material, more and more Nano material is applied to adsorbing domain.The constituent of nano material, scale topography are controllable, and possess larger ratio surface Product and homogeneous pore-size distribution, there is preferable adsorption capacity.The present invention is proposed in hollow ferroso-ferric oxide outer layer covers titanium dioxide The method of silica fibre, merge the advantages of by the two.Hollow ferroso-ferric oxide is a kind of nano material of excellent magnetic, is had super suitable Magnetic, can conveniently it be separated in the presence of externally-applied magnetic field；The nanometer silicon dioxide material of threadiness has larger ratio surface Product, the advantages that structure snd size are controllable, green.The core-shell structure threadiness nano SiO 2 particle being prepared both was gathered around There is larger specific surface area and can quickly to be separated by magnetic from solution.It can be repeated by water or washes of absolute alcohol after separation Utilize.
The content of the invention
It is an object of the invention to provide a kind of core-shell structure magnetic fibre shape nano SiO 2 particle and preparation method thereof And application.Concrete technical scheme provided by the invention is as follows：
A kind of core-shell structure magnetic fibre shape nano SiO 2 particle, using hollow ferroso-ferric oxide as kernel, fibrous two Silica is shell, and hollow ferroso-ferric oxide is prepared by hydro-thermal method, prepares to calcine after presoma by sol-gal process and obtains Core-shell structure magnetic fibre shape silica.
Further, the saturation magnetic intensity of the nano particle is 23 ~ 30emu/g, and specific surface area is 200 ~ 400m2/ g, Pore volume is 0.5 ~ 0.8cm3/ g, aperture are 8 ~ 20nm.
A kind of preparation method of above-mentioned core-shell structure magnetic fibre shape nano SiO 2 particle mainly includes：
（1）The preparation of hollow ferroferric oxide nano granules：Take mol ratio 1:3:150~1:10:180 Iron(III) chloride hexahydrate, Template and ethylene glycol mixing, while magnetic agitation, obtained mixture, which is put into hydrothermal synthesis reaction kettle, to be reacted.Reaction Obtained hollow ferroferric oxide nano granules are dried by Magnetic Isolation after alternately being cleaned with distilled water and absolute ethyl alcohol, Labeled as HFe3O4。
（2）The preparation of the ferroferric oxide nano granules of outer layer covers silica：By step（1）It is prepared HFe3O4It is added in the mixed solution of absolute ethyl alcohol, distilled water and ammoniacal liquor composition, at room temperature mechanical agitation 15min.Then will be with HFe3O4Solid-to-liquid ratio is 1:2~1:5 tetraethyl orthosilicate is added dropwise to 8 ~ 15h of mechanic whirl-nett reaction after mixed solution.Obtain The ferroferric oxide nano granules of outer layer covers silica alternately clean by Magnetic Isolation, and with distilled water and absolute ethyl alcohol After dry, labeled as HFe3O4@SiO2。
（3）The preparation of core-shell structure magnetic fibre shape nano SiO 2 particle：By step（2）The HFe being prepared3O4@ SiO20.5 ~ 2.5h of ultrasound forms solution A after nano particle is added to urea liquid.Cetyl trimethyl pyridine is dissolved in just The solution of amylalcohol and hexamethylene composition forms solution B.At room temperature will be with HFe3O4@SiO2Mass ratio is 4:1~7:1 positive silicic acid second Ester is added dropwise in the mixed solution that solution A forms with solution B, 0.5 ~ 2.5h of mechanical agitation.Then reacted at 100 ~ 140 DEG C Room temperature is down to after 3 ~ 8h, obtained nano particle is alternately cleaned, 40 ~ 60 DEG C by Magnetic Isolation with absolute ethyl alcohol and distilled water After drying 4 ~ 10h is calcined at 500 ~ 600 DEG C.Core-shell structure magnetic fibre shape nano SiO 2 particle is obtained, is labeled as HFe3O4@SiO2@KCC。
The step（1）In Iron(III) chloride hexahydrate used, ammonium salt and ethylene glycol mol ratio preferably 1:5:180~1:10: 180。
The step（1）In one kind in template used dose of preferred ammonium acetate, urea, lauryl amine.
The step（1）In 180-220 DEG C of hydrothermal synthesis reaction temperature used, preferably 190 ~ 210 DEG C, reaction time 10- 15h, preferably 10 ~ 13h.
The step（2）In HFe used3O4Solid-to-liquid ratio with absolute ethyl alcohol is 1:100~1:300g/mL, preferably 1:150~ 1:250g/mL, HFe3O4Solid-to-liquid ratio with distilled water is 1:50~1:70g/mL, preferably 1:50~1:60g/mL, HFe3O4With ammoniacal liquor Solid-to-liquid ratio be 6:3~8:3g/mL, preferably 6:3~8:3g/mL.
The step（2）In HFe used3O4With the solid-to-liquid ratio preferably 1 of tetraethyl orthosilicate:2~1:3 g/mL.
The step（2）In mechanic whirl-nett reaction time preferably 10 ~ 14h used.
The step（3）In HFe used3O4@SiO2Solid-to-liquid ratio with urea liquid is 1:100~1:150g/mL, preferably 1: 110~1:130g/mL, the concentration of urea used is 5 ~ 15g/L preferably 8 ~ 12g/L.
The step（3）In HFe used3O4@SiO2With the mass ratio preferably 1 of cetyl trimethyl pyridine:1~1:3.
The step（3）In cetyl trimethyl pyridine and n-amyl alcohol used solid-to-liquid ratio be 2:1~2:5, preferably 1:1~ 1:2, the solid-to-liquid ratio of cetyl trimethyl pyridine and hexamethylene is 1:40~1:80, preferably 1:50~1:70.
The step（3）In HFe used3O4@SiO2With the mass ratio preferably 1 of tetraethyl orthosilicate:4~1:6.
The step（3）In preferably 530 ~ 570 DEG C of calcining heat used, calcination time preferably 6 ~ 8h.
The present invention compared with prior art, there is following benefit：
1. a kind of core-shell structure magnetic fibre shape nano SiO 2 particle prepared by the present invention, while there is hollow four oxidation three The good characteristic of iron nano-particle and fibrous silica, available for fields such as sewage purifications.
2. a kind of core-shell structure magnetic fibre shape nano SiO 2 particle prepared by the present invention, specific surface area is 200 ~ 400m2/ g, pore volume and aperture are respectively 0.5 ~ 0.8cm3/ g and 8 ~ 20nm.Its outer layer is that fibrous silica is meso-hole structure, So that pollutant is attracted in abundant pore structure, there is preferable adsorption capacity.
3. a kind of core-shell structure magnetic fibre shape nano SiO 2 particle prepared by the present invention, its saturation magnetic intensity is 23 ~ 30emu/g, it can conveniently pass through Magnetic Isolation after absorption.
4. a kind of core-shell structure magnetic fibre shape nano SiO 2 particle raw material prepared by the present invention is cheap, operation Simplicity, products therefrom cost are relatively low.
Brief description of the drawings
Nitrogen suction-desorption curve of the products obtained therefrom of Fig. 1 embodiment of the present invention 5；
The graph of pore diameter distribution of the products obtained therefrom of Fig. 2 embodiment of the present invention 5；
The hysteresis curve of the products obtained therefrom of Fig. 3 embodiment of the present invention 5.
Embodiment
In order to preferably implement and understand the present invention, the present invention is further described below by specific embodiment.
Embodiment 1
（1）The preparation of hollow ferroferric oxide nano granules：Take mol ratio 1:5:160 Iron(III) chloride hexahydrate, urea and second Glycol is mixed, while magnetic agitation, and obtained mixture, which is put into hydrothermal synthesis reaction kettle, to be reacted, reaction temperature 220 DEG C, reaction time 10h.Obtained hollow ferroferric oxide nano granules are reacted by Magnetic Isolation, and with distilled water and anhydrous Ethanol is dried after alternately cleaning, labeled as HFe3O4。
（2）The preparation of the ferroferric oxide nano granules of outer layer covers silica：By step（1）It is prepared HFe3O4It is added in the mixed solution of absolute ethyl alcohol, distilled water and ammoniacal liquor composition, wherein HFe3O4With the solid-to-liquid ratio of absolute ethyl alcohol For 1:300g/mL, HFe3O4Solid-to-liquid ratio with distilled water is 1:50g/mL, HFe3O4Solid-to-liquid ratio with ammoniacal liquor is 9:3g/mL.Room The lower mechanical agitation 15min of temperature.Then will be with HFe3O4Solid-to-liquid ratio is 1:4 tetraethyl orthosilicate is added dropwise to machine after mixed solution Tool stirring reaction 12h.The ferroferric oxide nano granules of obtained outer layer covers silica by Magnetic Isolation, and with distillation Water and absolute ethyl alcohol are dried after alternately cleaning, labeled as HFe3O4@SiO2。
（3）The preparation of core-shell structure magnetic fibre shape nano SiO 2 particle：By step（2）The HFe being prepared3O4@ SiO2Ultrasonic 1h forms solution A, wherein HFe after nano particle is added to urea liquid3O4@SiO2With the solid-to-liquid ratio of urea liquid For 1:150g/mL, the concentration of urea liquid used is 5g/L.Cetyl trimethyl pyridine is dissolved in n-amyl alcohol and hexamethylene group Into solution formed solution B, wherein HFe3O4@SiO2Mass ratio with cetyl trimethyl pyridine is 1:1, cetyl three The solid-to-liquid ratio of picoline and n-amyl alcohol is 2:5, the solid-to-liquid ratio of cetyl trimethyl pyridine and hexamethylene is 1:40.At room temperature Will be with HFe3O4@SiO2Mass ratio is 5:1 tetraethyl orthosilicate is added dropwise in the mixed solution that solution A forms with solution B, machine Tool stirs 1.5h.Then room temperature is down to after reacting 5h at 120 DEG C, obtained nano particle is by Magnetic Isolation, with anhydrous second Alcohol and distilled water are alternately cleaned, and 7h is calcined at 540 DEG C after 40 DEG C of drying.Obtain core-shell structure magnetic fibre shape silica nanometer Particle, labeled as HFe3O4@SiO2@KCC。
（4）By gained HFe3O4@SiO2@KCC are used to adsorb organic dyestuff methylene blue：In 100mL, 5mg/L methylene The 2mgHFe that above method is prepared is added in blue solution3O4@SiO2@KCC adsorbents, it is real that Static Adsorption is carried out at room temperature Test, lucifuge reaction 30min, eliminating rate of absorption is up to 94%.
（5）The core-shell structure magnetic fibre shape nano SiO 2 particle progress nitrogen adsorption obtained to this experiment-de- Attached detection, it is 301.42m that can calculate specific surface area according to adsorpting data2/ g, pore volume 0.765cm3/ g, aperture are 15.23nm.Big specific surface area and abundant meso-hole structure cause magnetic fibre shape silica nanometer prepared by the present invention Grain has preferable absorption property.Magnetic saturation test is carried out, the saturation magnetic intensity of magnetic fibre shape nano SiO 2 particle is high Up to 25.36emu/g.
Embodiment 2
（1）The preparation of hollow ferroferric oxide nano granules：Take mol ratio 1:8:180 Iron(III) chloride hexahydrate, lauryl amine and Ethylene glycol is mixed, while magnetic agitation, and obtained mixture, which is put into hydrothermal synthesis reaction kettle, to be reacted, reaction temperature 200 DEG C, reaction time 12h.Obtained hollow ferroferric oxide nano granules are reacted by Magnetic Isolation, and with distilled water and anhydrous Ethanol is dried after alternately cleaning, labeled as HFe3O4。
（2）The preparation of the ferroferric oxide nano granules of outer layer covers silica：By step（1）It is prepared HFe3O4It is added in the mixed solution of absolute ethyl alcohol, distilled water and ammoniacal liquor composition, wherein, HFe3O4With the solid-liquid of absolute ethyl alcohol Than for 1:200g/mL, HFe3O4Solid-to-liquid ratio with distilled water is 1:60g/mL, HFe3O4Solid-to-liquid ratio with ammoniacal liquor is 7:3g/mL. Mechanical agitation 15min at room temperature.Then will be with HFe3O4Solid-to-liquid ratio is 1:After 5 tetraethyl orthosilicate is added dropwise to mixed solution Mechanic whirl-nett reaction 14h.The ferroferric oxide nano granules of obtained outer layer covers silica by Magnetic Isolation, and with steam Distilled water and absolute ethyl alcohol are dried after alternately cleaning, labeled as HFe3O4@SiO2。
（3）The preparation of core-shell structure magnetic fibre shape nano SiO 2 particle：By step（2）The HFe being prepared3O4@ SiO2Ultrasonic 2h forms solution A, wherein HFe after nano particle is added to urea liquid3O4@SiO2With the solid-to-liquid ratio of urea liquid For 1:120g/mL, the concentration of urea liquid used is 10g/L.Cetyl trimethyl pyridine is dissolved in n-amyl alcohol and hexamethylene The solution of composition forms solution B, wherein HFe3O4@SiO2Mass ratio with cetyl trimethyl pyridine is 1:2, middle hexadecane The solid-to-liquid ratio of base trimethylpyridine and n-amyl alcohol is 2:3, the solid-to-liquid ratio of cetyl trimethyl pyridine and hexamethylene is 1:60.Room Will be with HFe under temperature3O4@SiO2Mass ratio is 7:Solution A and the mixed solution of solution B composition is added dropwise in 1 tetraethyl orthosilicate In, mechanical agitation 1.5h.Then room temperature is down to after reacting 3h at 140 DEG C, obtained nano particle is by Magnetic Isolation, with nothing Water-ethanol and distilled water are alternately cleaned, and 4h is calcined at 580 DEG C after 60 DEG C of drying.Obtain core-shell structure magnetic fibre shape silica Nano particle, labeled as HFe3O4@SiO2@KCC。
（4）By the HFe of gained3O4@SiO2@KCC are used to adsorb organic dyestuff methyl orange：In 100mL, 30mg/L methyl The 20mgHFe that above method is prepared is added in orange solution3O4@SiO2@KCC adsorbents, it is real that Static Adsorption is carried out at room temperature Test, lucifuge reaction 30min, eliminating rate of absorption is up to 90%.
（5）The core-shell structure magnetic fibre shape nano SiO 2 particle progress nitrogen adsorption obtained to this experiment-de- Attached detection, it is 298.35m that can calculate specific surface area according to adsorpting data2/ g, pore volume 0.711cm3/ g, aperture are 16.89nm.Big specific surface area and abundant meso-hole structure cause magnetic fibre shape silica nanometer prepared by the present invention Grain has preferable absorption property.Magnetic saturation test is carried out, the saturation magnetic intensity of magnetic fibre shape nano SiO 2 particle is high Up to 27.13emu/g.
Embodiment 3
（1）The preparation of hollow ferroferric oxide nano granules：Take mol ratio 1:10:170 Iron(III) chloride hexahydrate, ammonium acetate and Ethylene glycol is mixed, while magnetic agitation, and obtained mixture, which is put into hydrothermal synthesis reaction kettle, to be reacted, reaction temperature 190 DEG C, reaction time 10h.Obtained hollow ferroferric oxide nano granules are reacted by Magnetic Isolation, and with distilled water and anhydrous Ethanol is dried after alternately cleaning, labeled as HFe3O4。
（2）The preparation of the ferroferric oxide nano granules of outer layer covers silica：By step（1）It is prepared HFe3O4It is added in the mixed solution of absolute ethyl alcohol, distilled water and ammoniacal liquor composition, wherein, HFe3O4With the solid-liquid of absolute ethyl alcohol Than for 1:150g/mL, HFe3O4Solid-to-liquid ratio with distilled water is 1:55g/mL, HFe3O4Solid-to-liquid ratio with ammoniacal liquor is 6:3g/mL. Mechanical agitation 15min at room temperature.Then will be with HFe3O4Solid-to-liquid ratio is 1:After 3 tetraethyl orthosilicate is added dropwise to mixed solution Mechanic whirl-nett reaction 9h.The ferroferric oxide nano granules of obtained outer layer covers silica by Magnetic Isolation, and with steam Distilled water and absolute ethyl alcohol are dried after alternately cleaning, labeled as HFe3O4@SiO2。
（3）The preparation of core-shell structure magnetic fibre shape nano SiO 2 particle：By step（2）The HFe being prepared3O4@ SiO2Ultrasonic 1h forms solution A, wherein HFe after nano particle is added to urea liquid3O4@SiO2With the solid-to-liquid ratio of urea liquid It is preferred that 1:110g/mL, the preferred 8g/L of concentration of urea used.Cetyl trimethyl pyridine is dissolved in n-amyl alcohol and hexamethylene group Into solution formed solution B, wherein HFe3O4@SiO2With the mass ratio preferably 1 of cetyl trimethyl pyridine:1, cetyl The solid-to-liquid ratio of trimethylpyridine and n-amyl alcohol preferably 1:1, the solid-to-liquid ratio preferably 1 of cetyl trimethyl pyridine and hexamethylene:50. At room temperature will be with HFe3O4@SiO2Mass ratio is 6:Solution A and the mixed solution of solution B composition is added dropwise in 1 tetraethyl orthosilicate In, mechanical agitation 2h.Then room temperature is down to after reacting 8h at 110 DEG C, obtained nano particle is anhydrous by Magnetic Isolation, use Ethanol and distilled water are alternately cleaned, and 10h is calcined at 550 DEG C after 50 DEG C of drying.Obtain core-shell structure magnetic fibre shape silica Nano particle, labeled as HFe3O4@SiO2@KCC。
（4）By gained HFe3O4@SiO2@KCC are used to adsorb hardly degraded organic substance terephthalic acid (TPA)：In 100mL, 20mg/L Terephthalic acid solution in add the 15mgHFe that is prepared of above method3O4@SiO2@KCC adsorbents, are carried out at room temperature Staticadsorption experiment, lucifuge reaction 30min, eliminating rate of absorption is up to 92%.
（5）The core-shell structure magnetic fibre shape nano SiO 2 particle progress nitrogen adsorption obtained to this experiment-de- Attached detection, it is 269.21m that can calculate specific surface area according to adsorpting data2/ g, pore volume 0.539cm3/ g, aperture are 18.23nm.Big specific surface area and abundant meso-hole structure cause magnetic fibre shape silica nanometer prepared by the present invention Grain has preferable absorption property.Magnetic saturation test is carried out, the saturation magnetic intensity of magnetic fibre shape nano SiO 2 particle is high Up to 25.97emu/g.
Embodiment 4
（1）The preparation of hollow ferroferric oxide nano granules：Take mol ratio 1:6:150 Iron(III) chloride hexahydrate, ammonium acetate and Ethylene glycol is mixed, while magnetic agitation, and obtained mixture, which is put into hydrothermal synthesis reaction kettle, to be reacted, and the reaction time is 13h, 210 DEG C of reaction temperature.Obtained hollow ferroferric oxide nano granules are reacted by Magnetic Isolation, and with distilled water and nothing Water-ethanol is dried after alternately cleaning, labeled as HFe3O4。
（2）The preparation of the ferroferric oxide nano granules of outer layer covers silica：By step（1）It is prepared HFe3O4It is added in the mixed solution of absolute ethyl alcohol, distilled water and ammoniacal liquor composition, wherein HFe3O4With the solid-to-liquid ratio of absolute ethyl alcohol It is preferred that 1:250g/mL, HFe3O4With the solid-to-liquid ratio preferably 1 of distilled water:60g/mL, HFe3O4With the solid-to-liquid ratio preferably 8 of ammoniacal liquor:3g/ ML mechanical agitation 15min at room temperature.Then will be with HFe3O4Solid-to-liquid ratio is 1:5 tetraethyl orthosilicate is added dropwise to mixed solution Mechanic whirl-nett reaction 15h afterwards.The ferroferric oxide nano granules of obtained outer layer covers silica are used in combination by Magnetic Isolation Distilled water and absolute ethyl alcohol are dried after alternately cleaning, labeled as HFe3O4@SiO2。
（3）The preparation of core-shell structure magnetic fibre shape nano SiO 2 particle：By step（2）The HFe being prepared3O4@ SiO2Ultrasonic 1.5h forms solution A, wherein HFe after nano particle is added to urea liquid3O4@SiO2With the solid-liquid of urea liquid Than preferably 1:130g/mL, the preferred 12g/L of concentration of urea used.Cetyl trimethyl pyridine is dissolved in n-amyl alcohol and hexamethylene The solution of alkane composition forms solution B, HFe3O4@SiO2With the mass ratio preferably 1 of cetyl trimethyl pyridine:3.Cetyl The solid-to-liquid ratio of trimethylpyridine and n-amyl alcohol preferably 1:2, the solid-to-liquid ratio preferably 1 of cetyl trimethyl pyridine and hexamethylene:70. At room temperature will be with HFe3O4@SiO2Mass ratio is 4:Solution A and the mixed solution of solution B composition is added dropwise in 1 tetraethyl orthosilicate In, mechanical agitation 2.5h.Then room temperature is down to after reacting 6h at 130 DEG C, obtained nano particle is by Magnetic Isolation, with nothing Water-ethanol and distilled water are alternately cleaned, and 5h is calcined at 600 DEG C after 60 DEG C of drying.Obtain core-shell structure magnetic fibre shape silica Nano particle, labeled as HFe3O4@SiO2@KCC。
（4）The HFe that will be obtained3O4@SiO2@KCC are used to adsorb hardly degraded organic substance phenol：In 100mL, 3mg/L phenol The 1mgHFe that above method is prepared is added in solution3O4@SiO2@KCC adsorbents, carry out Staticadsorption experiment at room temperature, Lucifuge reacts 30min, and eliminating rate of absorption is up to 93%.
（5）The core-shell structure magnetic fibre shape nano SiO 2 particle progress nitrogen adsorption obtained to this experiment-de- Attached detection, it is 223.48m that can calculate specific surface area according to adsorpting data2/ g, pore volume 0.603cm3/ g, aperture are 14.72nm.Big specific surface area and abundant meso-hole structure cause magnetic fibre shape silica nanometer prepared by the present invention Grain has preferable absorption property.Magnetic saturation test is carried out, the saturation magnetic intensity of magnetic fibre shape nano SiO 2 particle is high Up to 25.43emu/g.
Embodiment 5
（1）The preparation of hollow ferroferric oxide nano granules：Take mol ratio 1:3:180 Iron(III) chloride hexahydrate, ammonium acetate and Ethylene glycol is mixed, while magnetic agitation, and obtained mixture, which is put into hydrothermal synthesis reaction kettle, to be reacted, and reaction temperature is 180 DEG C, reaction time 15h.React obtained hollow ferroferric oxide nano granules by Magnetic Isolation, and with distilled water with Absolute ethyl alcohol is dried after alternately cleaning, labeled as HFe3O4。
（2）The preparation of the ferroferric oxide nano granules of outer layer covers silica：By step（1）It is prepared HFe3O4It is added in the mixed solution of absolute ethyl alcohol, distilled water and ammoniacal liquor composition, wherein HFe3O4With the solid-to-liquid ratio of absolute ethyl alcohol For 1:100g/mL, HFe3O4Solid-to-liquid ratio with distilled water is 1:70g/mL, HFe3O4Solid-to-liquid ratio with ammoniacal liquor is 5:3g/mL, room The lower mechanical agitation 15min of temperature.Then will be with HFe3O4Solid-to-liquid ratio is 1:2 tetraethyl orthosilicate is added dropwise to machine after mixed solution Tool stirring reaction 10h.The ferroferric oxide nano granules of obtained outer layer covers silica by Magnetic Isolation, and with distillation Water and absolute ethyl alcohol are dried after alternately cleaning, labeled as HFe3O4@SiO2。
（3）The preparation of core-shell structure magnetic fibre shape nano SiO 2 particle：By step（2）The HFe being prepared3O4@ SiO2Ultrasonic 1.5h forms solution A, wherein HFe after nano particle is added to urea liquid3O4@SiO2With the solid-liquid of urea liquid Than for 1:100g/mL, the concentration of urea liquid used is 15g/L.Cetyl trimethyl pyridine is dissolved in n-amyl alcohol and hexamethylene The solution of alkane composition forms solution B, wherein HFe3O4@SiO2Mass ratio with cetyl trimethyl pyridine is 1:3, hexadecane The solid-to-liquid ratio of base trimethylpyridine and n-amyl alcohol is 2:1, the solid-to-liquid ratio of cetyl trimethyl pyridine and hexamethylene is 1:80.Room Will be with HFe under temperature3O4@SiO2Mass ratio is 4:Solution A and the mixed solution of solution B composition is added dropwise in 1 tetraethyl orthosilicate In, mechanical agitation 1.5h.Then room temperature is down to after reacting 5h at 100 DEG C, obtained nano particle is by Magnetic Isolation, with nothing Water-ethanol and distilled water are alternately cleaned, and 6h is calcined at 500 DEG C after 50 DEG C of drying.Obtain core-shell structure magnetic fibre shape silica Nano particle, labeled as HFe3O4@SiO2@KCC。
（4）By gained HFe3O4@SiO2@KCC are used to adsorb organic dyestuff rhodamine B：In 100mL, 10mg/L rhodamine The 10mgHFe that above method is prepared is added in B solution3O4@SiO2@KCC adsorbents, it is real that Static Adsorption is carried out at room temperature Test, lucifuge reaction 30min, eliminating rate of absorption is up to 96%.
（5）The core-shell structure magnetic fibre shape nano SiO 2 particle progress nitrogen adsorption obtained to this experiment-de- Attached detection, as depicted in figs. 1 and 2, it is 229.96m that can calculate specific surface area according to adsorpting data to its result2/ g, pore volume are 0.567cm3/ g, aperture 17.53nm.Big specific surface area and abundant meso-hole structure cause magnetic fibre prepared by the present invention Shape nano SiO 2 particle has preferable absorption property.
（6）The core-shell structure magnetic fibre shape nano SiO 2 particle obtained to this experiment carries out magnetic saturation survey Examination, as a result as shown in figure 3, as seen from Figure 3, the saturation magnetic intensity of magnetic fibre shape nano SiO 2 particle is up to 26.21emu/g.Curve does not have any hysteresis simultaneously, shows that material has a superparamagnetism, synthesized by high saturation magnetic intensity explanation Magnetic fibre shape nano SiO 2 particle there is the segregative feature of magnetic.
Comparative example 1
（1）The preparation of hollow ferroferric oxide nano granules：Take mol ratio 1:3:180 Iron(III) chloride hexahydrate, ammonium acetate and Ethylene glycol is mixed, while magnetic agitation, and obtained mixture, which is put into hydrothermal synthesis reaction kettle, to be reacted, and reaction temperature is 180 DEG C, reaction time 15h.React obtained hollow ferroferric oxide nano granules by Magnetic Isolation, and with distilled water with Absolute ethyl alcohol is dried after alternately cleaning, labeled as HFe3O4。
（2）The preparation of the ferroferric oxide nano granules of outer layer covers silica：By step（1）It is prepared HFe3O4It is added in the mixed solution of absolute ethyl alcohol, distilled water and ammoniacal liquor composition, wherein HFe3O4With the solid-to-liquid ratio of absolute ethyl alcohol For 1:100g/mL, HFe3O4Solid-to-liquid ratio with distilled water is 1:70g/mL, HFe3O4Solid-to-liquid ratio with ammoniacal liquor is 5:3g/mL, room The lower mechanical agitation 15min of temperature.Then will be with HFe3O4Solid-to-liquid ratio is 1:2 tetraethyl orthosilicate is added dropwise to machine after mixed solution Tool stirring reaction 10h.The ferroferric oxide nano granules of obtained outer layer covers silica by Magnetic Isolation, and with distillation Water and absolute ethyl alcohol are dried after alternately cleaning, labeled as HFe3O4@SiO2。
（3）By gained HFe3O4@SiO2For adsorbing organic dyestuff rhodamine B：It is molten in 100mL, 10mg/L rhodamine B The 10mgHFe that above method is prepared is added in liquid3O4@SiO2Adsorbent, Staticadsorption experiment, lucifuge are carried out at room temperature 30min is reacted, eliminating rate of absorption is up to 33%.
The core-shell structure magnetic fibre shape nano SiO 2 particle prepared as the adsorbent of water pollutant, this patent Adsorption capacity is higher, adsorption effect is more preferable.Its hollow ferroso-ferric oxide kernel causes the adsorbent to be easy to separate from solution, The silica shells of threadiness cause the adsorbent to possess bigger specific surface area, and abundant pore structure causes the adsorbent to gather around There is bigger adsorption capacity.Silica has good chemical stability so that the adsorbent possesses good recycling Performance.

Claims (10)

1. a kind of core-shell structure magnetic fibre shape nano SiO 2 particle, it is characterised in that using hollow ferroso-ferric oxide be interior Core, fibrous silica are shell, prepare hollow ferroso-ferric oxide by hydro-thermal method, forerunner is prepared by sol-gal process Calcining obtains core-shell structure magnetic fibre shape silica after body.
2. core-shell structure magnetic fibre shape nano SiO 2 particle according to claim 1, it is characterised in that saturation magnetic Intensity is 23 ~ 30emu/g, and specific surface area is 200 ~ 400m2/ g, pore volume are 0.5 ~ 0.8cm3/ g, aperture are 8 ~ 20nm.
3. a kind of preparation method of any one of claim 1-2 core-shell structure magnetic fibre shape nano SiO 2 particles, It is characterised in that it includes following steps：
（1）The preparation of hollow ferroferric oxide nano granules：Take mol ratio 1:3:150~1:10:180 Iron(III) chloride hexahydrate, Template and ethylene glycol mixing, while magnetic agitation, obtained mixture, which is put into hydrothermal synthesis reaction kettle, to be reacted, reaction Obtained hollow ferroferric oxide nano granules are dried by Magnetic Isolation after alternately being cleaned with distilled water and absolute ethyl alcohol, Labeled as HFe3O4；
（2）The preparation of the ferroferric oxide nano granules of outer layer covers silica：By step（1）The HFe being prepared3O4Add Enter into the mixed solution of absolute ethyl alcohol, distilled water and ammoniacal liquor composition, at room temperature mechanical agitation 15min, then will be with HFe3O4Gu Liquor ratio is 1:2~1:5g/mL tetraethyl orthosilicate is added dropwise to 8 ~ 15h of mechanic whirl-nett reaction after mixed solution, obtained outer layer The ferroferric oxide nano granules of silica are wrapped up by Magnetic Isolation, and are dried after alternately being cleaned with distilled water and absolute ethyl alcohol It is dry, labeled as HFe3O4@SiO2；
（3）The preparation of core-shell structure magnetic fibre shape nano SiO 2 particle：By step（2）The HFe being prepared3O4@SiO2 0.5 ~ 2.5h of ultrasound forms solution A after nano particle is added to urea liquid；Cetyl trimethyl pyridine is dissolved in n-amyl alcohol Solution B is formed with the solution of hexamethylene composition, solution A is mixed with solution B, then at room temperature will be with HFe3O4@SiO2Mass ratio For 4:1~7:1 tetraethyl orthosilicate is added dropwise in the mixed solution that solution A forms with solution B, 0.5 ~ 2.5h of mechanical agitation, so Room temperature is down to after reacting 3 ~ 8h at 100 ~ 140 DEG C afterwards, obtained nano particle is by Magnetic Isolation, with absolute ethyl alcohol and distillation Water alternately cleans, and calcines 4 ~ 10h at 500 ~ 600 DEG C after 40 ~ 60 DEG C of drying, obtains core-shell structure magnetic fibre shape silica and receive Rice grain, labeled as HFe3O4@SiO2@KCC。
4. the preparation method of core-shell structure magnetic fibre shape nano SiO 2 particle according to claim 3, its feature It is：The step（1）In template be ammonium acetate, urea, one kind in lauryl amine.
5. the preparation method of core-shell structure magnetic fibre shape nano SiO 2 particle according to claim 3, its feature It is：The step（1）In hydrothermal synthesis reaction kettle in reaction condition be 180 ~ 220 DEG C of temperature, 10 ~ 15h of reaction time.
6. the preparation method of core-shell structure magnetic fibre shape nano SiO 2 particle according to claim 3, its feature It is：The step（2）Middle HFe3O4Solid-to-liquid ratio with absolute ethyl alcohol is 1:100~1:300g/mL, HFe3O4With consolidating for distilled water Liquor ratio is 1:50~1:70g/mL, HFe3O4Solid-to-liquid ratio with ammoniacal liquor is 5:3~9:3g/mL.
7. the preparation method of core-shell structure magnetic fibre shape nano SiO 2 particle according to claim 3, its feature It is：The step（3）Middle HFe3O4@SiO2Solid-to-liquid ratio with urea liquid is 1:100~1:150g/mL, urea liquid used Concentration be 5 ~ 15g/L.
8. the preparation method of core-shell structure magnetic fibre shape nano SiO 2 particle according to claim 3, its feature It is：The step（3）Middle HFe3O4@SiO2Mass ratio with cetyl trimethyl pyridine is 1:1~1:3.
9. the preparation method of core-shell structure magnetic fibre shape nano SiO 2 particle according to claim 3, its feature It is：The step（3）The solid-to-liquid ratio of middle cetyl trimethyl pyridine and n-amyl alcohol is 2:1~2:5, cetyl trimethyl The solid-to-liquid ratio of pyridine and hexamethylene is 1:40~1:80.
10. the core-shell structure magnetic fibre shape nano SiO 2 particle described in a kind of any one of claim 1-9 is adsorbing Application in water in hardly degraded organic substance.
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Application publication date: 20171121