CN105776350B - A kind of preparation method of hollow bar-shaped ferroso-ferric oxide and its compound - Google Patents
A kind of preparation method of hollow bar-shaped ferroso-ferric oxide and its compound Download PDFInfo
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- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide (Fe3O4)
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention discloses the preparation method of a kind of hollow bar-shaped ferroso-ferric oxide and its compound, bar-shaped silica is prepared first, using it as template, by different sources of iron in the template surface coated ferriferrous oxide or ferroferric oxide compound, etched again by sodium hydroxide and remove silica template, so as to obtain hollow bar-shaped ferroso-ferric oxide and its compound.The preparation condition of the present invention is gentle, simple to operate, can meet the needs of large-scale production；And the bar-shaped ferroso-ferric oxide and its compound being prepared have a hollow-core construction, light, not free settling, very big advantage is occupied in Responsive photonic crystals field；Add club shaped structure outside so that it has good anisotropy, so as to have the unexistent optical property of general spherical shape nano-particle, thus is had a wide range of applications in fields such as chemical industry, environment, national defence, especially suitable for Responsive photonic crystals field.
Description
Technical field
The present invention relates to nano-particle to synthesize field, the system of especially a kind of hollow bar-shaped ferroso-ferric oxide and its compound
Preparation Method.
Background technology
Ferroso-ferric oxide category cubic system, inverse spinel structure, it is a kind of important spinel type ferrite, widely deposits
It is nature, there is ferrimagnetism, while there is excellent electric conductivity again, makes it in medical treatment, electronic product, defence and military etc.
Field, have a wide range of applications.Because ferroso-ferric oxide has high refractive index and excellent optical property, thus often by with
In Responsive photonic crystals field, bar-shaped ferroso-ferric oxide with anisotropy due to becoming in Responsive photonic crystals
One new study hotspot.
At present, the synthetic method of bar-shaped ferroso-ferric oxide is mainly by by the iron such as di-iron trioxide or a hydrated iron
Intermediate, the methods of then passing through hydrogen reducing again, is so as to indirectly obtaining bar-shaped ferroso-ferric oxide.While in accordance with this side
Method can prepare bar-shaped ferroso-ferric oxide, but be significantly present of weak point：Preparation technology is more complicated first, is unfavorable for big
Large-scale production application；Second by hydrogen high temperature reduction, there is experiment condition is harsh and the dangerous property of experimentation etc. to be asked
Topic.
And for example one kind is disclosed in Publication No. CN103979613A Chinese patent literature prepare ferriferrous oxide nano
The method of rod, using a step solvent-thermal method, it can be formed using the hydrophilic and hydrophobic difference between hyperbranched polyglycidyl ether and oleic acid
Receive microstage micella/vesica, pass through the life of its bar-shaped " microreactor " limitation/guiding ferroso-ferric oxide crystal being self-assembly of
It is long, a diameter of 30~100nm is prepared for, length is 200~500nm ferriferrous oxide nano rod.Although the preparation method can
To prepare ferriferrous oxide nano rod by a step solvent method, but what is prepared is solid bar-shaped ferroso-ferric oxide, quality compared with
Weight, the application being unfavorable in Responsive photonic crystals field, and also nano-particle adjustable extent is narrower.
The content of the invention
The invention provides the preparation method of a kind of hollow bar-shaped ferroso-ferric oxide and its compound, this method prepares bar
Part is gentle, simple to operate, can meet the needs of large-scale production；And the bar-shaped ferroso-ferric oxide and its compound being prepared
With hollow-core construction, light, not free settling, very big advantage is occupied in Responsive photonic crystals field；Club shaped structure is added outside,
So that it has good anisotropy, so as to have the unexistent optical property of general spherical shape nano-particle.
The invention discloses a kind of preparation method of hollow bar-shaped ferroso-ferric oxide, comprise the following steps：
(1) polyvinylpyrrolidone mixes to obtain solution I with n-amyl alcohol, and ethanol, water, sodium citrate solution and ammoniacal liquor mix
Solution II, solution I is mixed with solution II, solution III is obtained after stirring；
(2) add tetraethyl orthosilicate in the solution III obtained to step (1), stand reaction, then post-treated obtain rod
Shape silica；
(3) bar-shaped silica is mixed with water, it is water-soluble that preparation obtains the bar-shaped silica that concentration is 0.5~50wt%
Liquid；
After two citric acid monohydrate trisodiums are mixed with ethylene glycol, add sodium acetate and deionized water obtains solution A, by
One source of iron mixes with ethylene glycol, adds bar-shaped aqueous silica solution and obtains solution B, solution A is mixed with solution B, through anti-
Should after obtain ferroso-ferric oxide cladding bar-shaped silica；
The first described source of iron is ferric trichloride, ferric acetyl acetonade, hexafluorophosphoric acid iron tricarbonyl；
(4) the bar-shaped silica that the ferroso-ferric oxide that step (3) obtains coats is mixed with sodium hydrate aqueous solution, water
It is post-treated to obtain hollow bar-shaped ferroso-ferric oxide after bath reaction.
Preferably, in step (1), the concentration of polyvinylpyrrolidone is 10~500g/L in solution I；；
Ethanol, water, the volume ratio of sodium citrate solution and ammoniacal liquor are 10:2~9:1:1~3；
The concentration of sodium citrate solution is 0.01~2mol/L, and the mass percent concentration of ammoniacal liquor is 25~28wt%；
The volume ratio of solution I and solution II is 0.6~64.
Preferably, the mixed process in step (1) is carried out under ultrasonic wave added more, ultrasound contributes to polyvinylpyrrolidine
Ketone is scattered in n-amyl alcohol, and the size of ultrasonic power forms influence the size of emulsion droplet, so as to influence the bar-shaped oxygen of generation
The size of SiClx；
Preferably, in step (2), the concentration of tetraethyl orthosilicate is 0.5~80g/L in solution III；
Preferably, in step (2), dwell temperature is 0~100 DEG C, and the time is 5min~20h.Reaction is stood in constant temperature
Carry out, rather than stood in atmosphere under water-bath because the temperature difference in different solar terms room has tens degree, the morning and evening temperature difference also compared with
Greatly, it is sufficient to have influence on the pattern and the uniformity of the bar-shaped silica of product.Water bath with thermostatic control is exactly to generate bar-shaped silica
Process provides an isoperibol, so caused by bar-shaped silica ability than more uniform and there is good pattern.
In the present invention, dwell temperature mainly influences the diameter and pattern of bar-shaped silica, at different temperature, can
To obtain the bar-shaped silica of different-diameter.Appropriate control temperature can also prepare the silica dioxide nano particle of different-shape
Son.Time of repose mainly has influence on the length of bar-shaped silica, and different length can be obtained under different time of repose
Bar-shaped silica.
Further preferably, dwell temperature is 40~80 DEG C, bar-shaped silica is prepared, and uniformity is more preferable.Temperature
It is too low, shorter stick shape silica, or even the irregular spherical silica of generation is prepared；Temperature is too high, obtains longer bar-shaped
Silica even generates silica white nano-wire.
Preferably, in step (3), the mass ratio of two citric acid monohydrate trisodiums and sodium acetate is 0.01~2, the solution
In A, the concentration of two citric acid monohydrate trisodiums is 0.005~0.5mol/L；
In the solution B, the concentration of the first source of iron is 2~655g/L, ethylene glycol and bar-shaped aqueous silica solution body
Product is than being 2~100；
The volume ratio of solution A and solution B is 0.2~20；
The temperature of the reaction is 100~400 DEG C, and the time is 4~48h.
Preferably, in step (4), the concentration of the sodium hydrate aqueous solution is 0.1~20mol/L；
Mole of the bar-shaped silica and sodium hydroxide in sodium hydrate aqueous solution of ferroso-ferric oxide-carbon complex cladding
Than less than 0.5；
The temperature of the water-bath is 10~100 DEG C, and the time is not less than 1h.
The invention also discloses a kind of preparation method of hollow bar-shaped ferroferric oxide compound, comprise the following steps：
(1) polyvinylpyrrolidone mixes to obtain solution I with n-amyl alcohol, and ethanol, water, sodium citrate solution and ammoniacal liquor mix
Solution II, solution I is mixed with solution II, solution III is obtained after stirring；
(2) add tetraethyl orthosilicate in the solution III obtained to step (1), stand reaction, then post-treated obtain rod
Shape silica；
(3) bar-shaped silica is mixed with water, it is water-soluble that preparation obtains the bar-shaped silica that concentration is 0.5~50wt%
Liquid；
Second source of iron, bar-shaped aqueous silica solution are mixed with organic solvent, oxidant is added after uniform, it is reacted
The bar-shaped silica of ferroso-ferric oxide-carbon complex cladding is obtained afterwards；
The second described source of iron is ferrocene, tri-iron dodecacarbonyl, ferrous sulfate；
(4) the bar-shaped silica of the ferroso-ferric oxide for obtaining step (3)-carbon complex cladding and sodium hydroxide are water-soluble
Liquid mixes, post-treated to obtain hollow bar-shaped ferroso-ferric oxide after water-bath.
Preferably, in step (1), the concentration of polyvinylpyrrolidone is 10~500g/L in solution I；
Ethanol, water, the volume ratio of sodium citrate solution and ammoniacal liquor are 10:2~9:1:1~3；
The concentration of sodium citrate solution is 0.01~2mol/L, and the mass percent concentration of ammoniacal liquor is 25~28wt%；
The volume ratio of solution I and solution II is 0.6~64；
In step (2), the concentration of tetraethyl orthosilicate is 0.5~80g/L in solution III；
The temperature for standing reaction is 0~100 DEG C, and the time is 10min~20h.
Preferably, in step (3), described organic solvent is acetone, dichloro-benzenes, toluene；Oxidant is hydrogen peroxide, nitre
Sour, high potassium chloride；
The volume ratio of the bar-shaped aqueous silica solution, organic solvent and oxidant is 0.5~5:60:2；
Second source of iron and the mass volume ratio of bar-shaped aqueous silica solution are 0.02~2g/ml；
Preferably, in step (3), the reaction is carried out in autoclave, is warming up to 50~150 DEG C first, is protected
After 10~48h of temperature, then 100~300 DEG C are warming up to, continue 10~48h of insulation；The purpose to heat up step by step is to prevent the life of accessory substance
Into, such as ferroso-ferric oxide bag carbon nano-particles.
Preferably, the concentration of the sodium hydrate aqueous solution is 0.1~20mol/L；
Mole of the bar-shaped silica and sodium hydroxide in sodium hydrate aqueous solution of ferroso-ferric oxide-carbon complex cladding
Than less than 0.5；
The temperature of the water-bath is 10~100 DEG C, and the time is not less than 1h.
Compared with prior art, the invention has the advantages that：
(1) preparation technology of the present invention is easy, cost is cheap；
(2) experiment condition of the present invention is gentle, without processes such as high-temperature hydrogen reductions；
(3) hollow bar-shaped ferroso-ferric oxide and its compound prepared by the present invention has anisotropy, and because is hollow
, there is the advantages of light weight, solid foundation has been established in application in Responsive photonic crystals field for it；And the chi of hollow granule
It is very little to regulate and control from nanoscale to micron order.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) photo of hollow bar-shaped ferroso-ferric oxide prepared by embodiment 1；
Fig. 2 is SEM (SEM) photo of bar-shaped silica prepared by embodiment 1；
Fig. 3 is transmission electron microscope (TEM) photo of hollow bar-shaped ferroso-ferric oxide prepared by embodiment 1；
Fig. 4 is X-ray diffraction (XRD) photo of hollow bar-shaped ferroso-ferric oxide-carbon complex prepared by embodiment 4；
Fig. 5 is that the transmission electron microscope (TEM) of hollow bar-shaped ferroso-ferric oxide-carbon complex prepared by embodiment 4 shines
Piece.
Embodiment
Embodiment 1
Polyvinylpyrrolidone (number-average molecular weight 4000) 15.00g is taken, n-amyl alcohol 150ml, ultrasonic dissolution, is well mixed
15ml ethanol is added afterwards, 4.2ml water, 1.5ml 0.18mol/L sodium citrate solutions, is shaken up manually, is added 3ml ammoniacal liquor (matter
Percent concentration is measured 26%), after shaking up manually, to add 1.5ml tetraethyl orthosilicates (TEOS), after shaking up manually, 40 DEG C of water
Bath, 30min is stood, take out centrifugation, washing obtains bar-shaped silica；
0.318g two citric acid monohydrate trisodiums are dissolved in 20ml ethylene glycol, add 1.5g anhydrous sodium acetate and
0.75g deionized water, is designated as solution A；0.819g ferric sesquichlorides are dissolved in 10ml ethylene glycol, continuously add 0.5ml
The bar-shaped aqueous silica solutions of 5wt%, are designated as solution B；Solution A is mixed with solution B, stirring makes it obtain palm fibre after being sufficiently mixed
Dark clear solution is simultaneously positioned in the high-temperature high-pressure reaction kettle that volume is 50ml, and it is 200 DEG C to set temperature, and at such a temperature
React 10h.Obtained mixed solution is separated, washed by question response after terminating, you can obtains the rod of ferroso-ferric oxide cladding
Shape silica.
The bar-shaped silica that ferroso-ferric oxide coats is dissolved in 5mol/L sodium hydrate aqueous solution, in 55 DEG C of water-baths
Lower magnetic agitation reacts 10h.Question response centrifuges after terminating, with deionized water and washes of absolute alcohol for several times, you can obtain
Final products.
Fig. 1 is the XRD for the final products that the present embodiment is prepared, and as seen from the figure, the composition of product is four oxidations three
Iron.
Fig. 2 is the SEM figures for the bar-shaped silica that the present embodiment is prepared, and as seen from the figure, bar-shaped silica is put down
A diameter of 190~210nm, average length are 550~650nm；
Fig. 3 is the TEM figures for the final products that the present embodiment is prepared, and as seen from the figure, product is hollow club shaped structure, is made
Thickness for the ferroso-ferric oxide of clad is about 16~23nm.
Embodiment 2
Polyvinylpyrrolidone (number-average molecular weight 4000) 15.00g is taken, n-amyl alcohol 150ml, ultrasonic dissolution, is well mixed
15ml ethanol is added afterwards, 4.2ml water, 1.5ml 0.18mol/L sodium citrate solutions, is shaken up manually, is added 3.5ml ammoniacal liquor
(mass percent concentration 26%), after shaking up manually, add 1.5ml tetraethyl orthosilicates (TEOS), after shaking up manually, 40 DEG C
Water-bath, 30min is stood, take out centrifugation, washing obtains bar-shaped silica；
0.318g two citric acid monohydrate trisodiums are dissolved in 20ml ethylene glycol, add 1.5g anhydrous sodium acetate and
0.75g deionized water, is designated as solution A；0.819g ferric sesquichlorides are dissolved in 10ml ethylene glycol, continuously add 0.5ml
The bar-shaped aqueous silica solutions of 5wt%, are designated as solution B；Solution A is mixed with solution B, stirring makes it obtain palm fibre after being sufficiently mixed
Dark clear solution is simultaneously positioned in the high-temperature high-pressure reaction kettle that volume is 50ml, and it is 200 DEG C to set temperature, and at such a temperature
React 10h.Obtained mixed solution is separated, washed by question response after terminating, you can obtains the rod of ferroso-ferric oxide cladding
Shape silica.
The bar-shaped silica that ferroso-ferric oxide coats is dissolved in 5mol/L sodium hydrate aqueous solutions, under 55 DEG C of water-baths
Magnetic agitation reacts 10h.Question response centrifuges after terminating, with deionized water and washes of absolute alcohol for several times, you can produced
Product.
The present embodiment increases the addition of polyvinylpyrrolidone to 25g, increased simultaneously when preparing bar-shaped silica
The addition of ammoniacal liquor to 3.5ml, the pattern of the bar-shaped silica and final products that are prepared with the class in embodiment 1
Seemingly, difference is only that length is reduced to 400~430nm.
Embodiment 3
Polyvinylpyrrolidone (number-average molecular weight 4000) 35.00g is taken, n-amyl alcohol 150ml, ultrasonic dissolution, is well mixed
15ml ethanol is added afterwards, 4.2ml water, 1ml 0.18mol/L sodium citrate solutions, is shaken up manually, is added 3ml ammoniacal liquor (quality
Percent concentration is 26%), after shaking up manually, to add 1.5ml tetraethyl orthosilicates (TEOS), after shaking up manually, 40 DEG C of water-baths,
30min is stood, takes out centrifugation, washing obtains bar-shaped silica；
0.318g two citric acid monohydrate trisodiums are dissolved in 20ml ethylene glycol, add 1.5g anhydrous sodium acetate and
0.75g deionized water, is designated as solution A；0.819g ferric sesquichlorides are dissolved in 10ml ethylene glycol, continuously add 0.5ml
The bar-shaped aqueous silica solutions of 5wt%, are designated as solution B；Solution A is mixed with solution B, stirring makes it obtain palm fibre after being sufficiently mixed
Dark clear solution is simultaneously positioned in the high-temperature high-pressure reaction kettle that volume is 50ml, and it is 200 DEG C to set temperature, and at such a temperature
React 10h.Obtained mixed solution is separated, washed by question response after terminating, you can obtains the rod of ferroso-ferric oxide cladding
Shape silica.
The bar-shaped silica that ferroso-ferric oxide coats is dissolved in 5mol/L sodium hydrate aqueous solution, in 55 DEG C of water-baths
Lower magnetic agitation reacts 10h.Question response centrifuges after terminating, with deionized water and washes of absolute alcohol for several times, you can obtain
Final products.
The present embodiment increases the addition of polyvinylpyrrolidone to 35g, reduces lemon when preparing bar-shaped silica
The addition of acid sodium solution to 1ml, the pattern of the bar-shaped silica and final products that are prepared with the class in embodiment 1
Seemingly, difference is only that length is reduced to 290~320nm.
Embodiment 4
Polyvinylpyrrolidone (number-average molecular weight 4000) 15.00g is taken, n-amyl alcohol 150ml, ultrasonic dissolution, mixing is
15ml ethanol, 4.2ml water and the sodium citrate solution that 1.5ml concentration is 0.18mol/L are added after even, shakes up, adds manually
3ml ammoniacal liquor (mass percent concentration 26%), after shaking up manually, 1.5ml tetraethyl orthosilicates (TEOS) are added, are shaken up manually
Afterwards, 40 DEG C of water-baths, static 30min, centrifuged after taking-up, washing obtains bar-shaped silica；
0.1g ferrocene is taken, the bar-shaped aqueous silica solutions of 0.5ml 5wt%, 30ml acetone, ultrasonic mixing, is well mixed
1ml hydrogen peroxide is added afterwards, is fitted into after being uniformly mixed in 50ml autoclaves, is warming up to 100 DEG C first, after being incubated 24h
180 DEG C are warming up to again, continue to be incubated 24h, reaction terminates rear separating, washing, you can obtains ferroso-ferric oxide-carbon complex bag
The bar-shaped silica covered；
The bar-shaped silica of ferroso-ferric oxide-carbon complex cladding is dissolved in 5mol/L sodium hydrate aqueous solution,
Magnetic agitation reacts 10h under 55 DEG C of water-baths.Question response centrifuges after terminating, with deionized water and washes of absolute alcohol number
It is secondary, you can to obtain final products.
Fig. 4 is the XRD for the final products that the present embodiment is prepared, and as seen from the figure, the composition of product is four oxidations three
The compound of iron and carbon.
Fig. 5 is the TEM figures for the final products that the present embodiment is prepared, and as seen from the figure, product is hollow club shaped structure, and
Ferroso-ferric oxide is coated on carbon surface, has core shell structure, the thickness of clad is 55~65nm.
Embodiment 5
Polyvinylpyrrolidone (number-average molecular weight 4000) 15.00g is taken, n-amyl alcohol 150ml, ultrasonic dissolution, mixing is
15ml ethanol, 4.5ml water and the sodium citrate solution that 1.5ml concentration is 0.18mol/L are added after even, shakes up, adds manually
3ml ammoniacal liquor (mass percent concentration 26%), after shaking up manually, 1.5ml tetraethyl orthosilicates (TEOS) are added, are shaken up manually
Afterwards, 40 DEG C of water-baths, static 2h, centrifuged after taking-up, washing obtains bar-shaped silica；
0.1g ferrocene is taken, the bar-shaped aqueous silica solutions of 0.5ml 5wt%, 30ml acetone, ultrasonic mixing, is well mixed
1ml hydrogen peroxide is added afterwards, is fitted into after being uniformly mixed in 50ml autoclaves, is warming up to 100 DEG C first, after being incubated 24h
180 DEG C are warming up to again, continue to be incubated 24h, reaction terminates rear separating, washing, you can obtains ferroso-ferric oxide-carbon complex bag
The bar-shaped silica covered；
The bar-shaped silica of ferroso-ferric oxide-carbon complex cladding is dissolved in 5mol/L sodium hydrate aqueous solution,
Magnetic agitation reacts 10h under 55 DEG C of water-baths.Question response centrifuges after terminating, with deionized water and washes of absolute alcohol number
It is secondary, you can to obtain final products.
The present embodiment extends water-bath time of repose when preparing bar-shaped silica, and increases the addition of water extremely
4.5ml, the bar-shaped silica being prepared is similar with embodiment 4 with the pattern of final products, and diameter does not change,
Only it is that length increase is 1.7~1.9um.
Embodiment 6
Polyvinylpyrrolidone (number-average molecular weight 4000) 15.00g is taken, n-amyl alcohol 150ml, ultrasonic dissolution, mixing is
15ml ethanol, 4.2ml water and the sodium citrate solution that 1.5ml concentration is 0.18mol/L are added after even, shakes up, adds manually
3ml ammoniacal liquor (mass percent concentration 26%), after shaking up manually, 1.5ml tetraethyl orthosilicates (TEOS) are added, are shaken up manually
Afterwards, 60 DEG C of water-baths, static 30min, centrifuged after taking-up, washing obtains bar-shaped silica；
0.1g ferrocene is taken, the bar-shaped aqueous silica solutions of 0.5ml 5wt%, 30ml acetone, ultrasonic mixing, is well mixed
1ml hydrogen peroxide is added afterwards, is fitted into after being uniformly mixed in 50ml autoclaves, is warming up to 100 DEG C first, after being incubated 24h
180 DEG C are warming up to again, continue to be incubated 24h, reaction terminates rear separating, washing, you can obtains ferroso-ferric oxide-carbon complex bag
The bar-shaped silica covered；
The bar-shaped silica of ferroso-ferric oxide-carbon complex cladding is dissolved in 5mol/L sodium hydrate aqueous solution,
Magnetic agitation reacts 10h under 55 DEG C of water-baths.Question response centrifuges after terminating, with deionized water and washes of absolute alcohol number
It is secondary, you can to obtain final products.
The present embodiment improves water-bath dwell temperature to 60 DEG C, what is be prepared is bar-shaped when preparing bar-shaped silica
Silica is similar with embodiment 4 with the pattern of final products, and difference is only that diameter is reduced to 160~170nm or so,
Length increases to 0.8~1um.
Embodiment 7
Polyvinylpyrrolidone (number-average molecular weight 4000) 15.00g is taken, n-amyl alcohol 150ml, ultrasonic dissolution, mixing is
20ml ethanol, 4.2ml water and the sodium citrate solution that 1.5ml concentration is 0.18mol/L are added after even, shakes up, adds manually
3ml ammoniacal liquor (mass percent concentration 26%), after shaking up manually, 1.5ml tetraethyl orthosilicates (TEOS) are added, are shaken up manually
Afterwards, 80 DEG C of water-baths, static 30min, centrifuged after taking-up, washing obtains bar-shaped silica；
0.1g ferrocene is taken, the bar-shaped aqueous silica solutions of 0.5ml 5wt%, 30ml acetone, ultrasonic mixing, is well mixed
1ml hydrogen peroxide is added afterwards, is fitted into after being uniformly mixed in 50ml autoclaves, is warming up to 100 DEG C first, after being incubated 24h
180 DEG C are warming up to again, continue to be incubated 24h, reaction terminates rear separating, washing, you can obtains ferroso-ferric oxide-carbon complex bag
The bar-shaped silica covered；
The bar-shaped silica of ferroso-ferric oxide-carbon complex cladding is dissolved in 5mol/L sodium hydrate aqueous solution,
Magnetic agitation reacts 10h under 55 DEG C of water-baths.Question response centrifuges after terminating, with deionized water and washes of absolute alcohol number
It is secondary, you can to obtain final products.
The present embodiment improves water-bath dwell temperature to 80 DEG C when preparing bar-shaped silica, and increases adding for ethanol
For dosage to 20ml, the bar-shaped silica being prepared is similar with embodiment 4 with the pattern of final products, and difference is only
Diameter is reduced to 145~155nm, and length increases to 1.7~2.0um.
Claims (3)
1. a kind of preparation method of hollow bar-shaped ferroso-ferric oxide, it is characterised in that comprise the following steps：
(1) polyvinylpyrrolidone mixes to obtain solution I with n-amyl alcohol, and ethanol, water, sodium citrate solution and ammoniacal liquor mix to obtain solution
II, solution I is mixed with solution II, solution III is obtained after stirring；
(2) add tetraethyl orthosilicate in the solution III obtained to step (1), stand reaction, then post-treated obtain bar-shaped two
Silica；
The temperature for standing reaction is 40~80 DEG C, and the time is 10min~20h, stands reaction and is carried out under water bath with thermostatic control；
(3) bar-shaped silica is mixed with water, prepares and obtain the bar-shaped aqueous silica solution that concentration is 0.5~50wt%；
After two citric acid monohydrate trisodiums are mixed with ethylene glycol, add sodium acetate and water obtains solution A, by the first source of iron and second
Glycol mixes, and adds bar-shaped aqueous silica solution and obtains solution B, solution A is mixed with solution B, four are obtained after reacted
The bar-shaped silica of Fe 3 O cladding；
The first described source of iron is ferric trichloride, ferric acetyl acetonade or hexafluorophosphoric acid iron tricarbonyl；
The mass ratio of the two citric acid monohydrate trisodiums and sodium acetate is 0.01~2, in the solution A, two citric acid monohydrates three
The concentration of sodium is 0.005~0.5mol/L；
In the solution B, the concentration of the first source of iron is 2~655g/L, ethylene glycol and bar-shaped aqueous silica solution volume ratio
For 2~100；
The volume ratio of solution A and solution B is 0.2~20；
The temperature of the reaction is 100~400 DEG C, and the time is 4~48h；
(4) the bar-shaped silica that the ferroso-ferric oxide that step (3) obtains coats is mixed with sodium hydrate aqueous solution, water-bath is anti-
Ying Hou, it is post-treated to obtain hollow bar-shaped ferroso-ferric oxide.
2. the preparation method of hollow bar-shaped ferroso-ferric oxide according to claim 1, it is characterised in that molten in step (1)
The concentration of polyvinylpyrrolidone is 10~500g/L in liquid I；
Ethanol, water, the volume ratio of sodium citrate solution and ammoniacal liquor are 10:2~9:1:1~3；
The concentration of sodium citrate solution is 0.01~2mol/L, and the mass percent concentration of ammoniacal liquor is 25~28wt%；
The volume ratio of solution I and solution II is 0.6~64：1；
In step (2), the concentration of tetraethyl orthosilicate is 0.5~80g/L in solution III.
3. the preparation method of hollow bar-shaped ferroso-ferric oxide according to claim 1, it is characterised in that in step (4), institute
The concentration for stating sodium hydrate aqueous solution is 0.1~20mol/L；
The bar-shaped silica of ferroso-ferric oxide cladding is less than 0.5 with the mol ratio of sodium hydroxide in sodium hydrate aqueous solution；
The temperature of the water-bath is 10~100 DEG C, and the time is not less than 1h.
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