CN102976416A - Preparation method of hollow superparamagnetic nanospheres - Google Patents
Preparation method of hollow superparamagnetic nanospheres Download PDFInfo
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Abstract
The invention relates to a preparation method of hollow superparamagnetic nanospheres. The preparation method comprises the following steps: (1) pretreating cellulose raw materials through alkali liquor, soaking in oxidizing salt solution, and then hydrolyzing to obtain carboxyl cellulose nanospheres; (2) dispersing the cellulose nanospheres into water, adding little organic solvent and uniformly stirring, then sequentially adding ferric salt and ferrous salt, dropping alkali to react, and collecting the product by a magnet, so as to obtain the superparamagnetic nanospheres; and (3) roasting the superparamagnetic nanospheres at high temperature under inert atmosphere, so as to obtain the hollow magnetic nanospheres. The preparation method is simple, convenient and green in preparation technology, free from expensive equipment, wide in source of raw materials for production, low in cost and easy for mass production; and the hollow magnetic nanospheres prepared by the preparation method are higher in superparamagnetic response, controllable in dimension and uniform in chemical components, and can be applied to the fields such as the sewage treatment filed, the catalysis field, the magnetofluid field, the microwave absorption filed, the drug carrier filed, the biological enzyme fixation field and the biosensor field.
Description
Technical field
The invention belongs to the preparation field of magnetic Nano material, be specifically related to a kind of preparation method of hollow super-paramagnetism nano ball.
Background technology
Magnetic Nano Z 250 (Fe
30
4) because particle diameter is little, specific surface is larger, the chemically reactive of interface atom is high, adds the ferromagnetism of Z 250 own, fixes at magnetic fluid, microwave absorbing, sewage disposal, catalysis, pharmaceutical carrier, biological enzyme, there is good application prospect the aspect such as biosensor.Such as Fe
30
4Can be used for the magnetic resonance image-forming diagnose contrast medium at biological and field of medicaments, tissue repair, immunity, the magnetic targeting drug administration preparation, cell separation technology and biomolecules are solidified team etc.But the properties and applications of Z 250 is subjected to the impact of size of particles and pattern to a great extent.As medical material, the particle diameter of inorganic magnetic nano material should be less than 1O0nm usually, generally is advisable between 10～20nm, so relatively is conducive to be excreted safely.And as the catalyzer of nanoscale, its catalytic activity obviously is better than the respective masses material, this be because nano material to have specific surface area large, surface smoothness is poor, form rough atomic steps, be easier in reaction and the characteristics such as reactant fully contacts, can utilize magnetic separation technique, easily catalyzer is separated from half homogeneous system, keep the high reactivity of catalysis and realization to recycle.When studies show that the diameter that also shows when the inorganic magnetic material is less than 30nm, just had superparamagnetism.Magnetic particle with superparamagnetism is adding under the action of a magnetic field, has stronger magnetic, and can be subjected to the control of externally-applied magnetic field and move, when doing the time spent without externally-applied magnetic field, the very fast disappearance of magnetic, thus agglomeration can not occur because self has magnetic.In recent years, nanostructure Fe
3O
4Tiny balloon has the characteristic of low density, high-ratio surface, and its hollow parts can hold a large amount of guest molecules or large-sized object, so that it has important application prospect and receive much attention (CN1528675, CN101698516B) in many technical fields such as microwave absorbing material and medicine transmission.
Common preparation method has the precipitator method (CN101353181A), solvent-thermal method (CN101698516B, CN102153150A) and emulsion method (CN 101444712B, CN100573756C, CN102372307A) etc.The magnetic Fe that this several method makes
3O
4Nanocrystalline have certain difference in structure and aspect of performance, compares other method, and precipitator method synthetic operation is simple, temperature of reaction is low, the preparation magnetic Fe
3O
4Nanocrystalline have the advantages such as raw material is easy to get, particle purity high, and cost is relatively low, but the difficult control of products obtained therefrom size distribution.The problems such as and other several method more or less exists cost height, complex process, and products therefrom is reunited serious, and uniform particles is poor.Because Fe
3O
4There is the problem of reuniting mostly in the magnetic of self in Liquid preparation methods, restricted the performance of the physics and chemistry characteristic of Z 250 uniqueness.Therefore with Fe
3O
4Particulate load is to suitable base material, and maintenance Fe
3O
4The nano-meter characteristic of particle is very important.Preparing hollow ball method commonly used is exactly template, is about to ferriferrous oxide nano-particle and adopts the method for physics or chemistry to be adsorbed on polymer microsphere surface, then obtains hollow structure by high temperature sintering.The Marvin's wise man waits people (CN1528675) to utilize the polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer as template, adopt coprecipitation method to prepare hollow super paramagnetic ferriferrous oxide nano fine grain, size average out to 55～75nm, the thickness of shell is about 5nm, but the triblock copolymer price that adopts is higher.Want easy, high yield, low cost, the hollow magnetic nanometer ball that can produce in batches simultaneously just need to find the template that a kind of size is controlled, machinery is good with chemical stability, preparation process is relative simply, surface functional group enriches.Mierocrystalline cellulose wide material sources, cheap, and contain a large amount of active groups, there is part Study person to carry out magnetic nano-particle and Mierocrystalline cellulose compound, send out congruence (CN101942103A) such as analogy the superparamagnetism magnetic particle is joined in the cellulose solution, made the cellulose magnetic microsphere that is of a size of 0.1～100 μ m with the electrostatic spraying technology; Then take the aqueous solution of alkali/urea or thiocarbamide as solvent, adopt direct entrapping method to prepare the magnetic cellulose microsphere particle diameter is 1～600 μ m to Zhang Lina etc. (CN 101274985B).The magnetic particle size that these preparation methods obtain is larger, and saturation magnetization is low, has limited to a certain extent its application.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of hollow super-paramagnetism nano ball, the easy green of the method manufacture craft, does not need expensive extensive, with low cost, the easy large-scale production of equipment, raw material sources; Prepared hollow magnetic nanometer ball has the response of higher superparamagnetic, size is controlled, chemical constitution is even, can be used for the fields such as sewage disposal, catalysis, magnetic fluid, microwave absorbing, pharmaceutical carrier, biological enzyme are fixed, biosensor.
The preparation method of a kind of hollow super-paramagnetism nano ball of the present invention comprises:
(1) cellulosic material is soaked 30～60min in the NaOH of 1mol/L solution, water immerses in the oxidisability salts solution after cleaning again, and 60～90 ℃ of lower hydrolysis 8～16h obtain carboxylated cellulose nanospheres; The mass ratio of cellulosic material and oxidisability salt is 1:5～10;
(2) above-mentioned cellulose nanospheres is distributed in the water, adds organic solvent, after stirring, add successively trivalent iron salt and divalent iron salt, drip again 20～60 ℃ of lower reaction 1～5h of alkali lye, and with magnet product is collected, obtain magnetic nano composite microsphere; Organic solvent accounts for 1～7% of cumulative volume, and the mol ratio of trivalent iron salt, divalent iron salt and alkali is 2:1:1～3;
(3) in inert atmosphere, magnetic nano composite microsphere is calcined at 400 ℃～1000 ℃, obtained the hollow magnetic nanometer ball.
Cellulosic material in the described step (1) is regenerated cellulose fibre, has been selected from copper ammonia fibre, viscose fiber or saponified acetate.
Oxidisability salt in the described step (1) is persulphate, permanganate or dichromate, and the concentration of oxidisability salt brine solution is 1～2.5mol/L.
Persulphate in the described step (1) is ammonium persulphate; Permanganate is potassium permanganate; Dichromate is potassium bichromate.
The solid content of cellulose nanospheres in dispersion liquid in the described step (2) is 10～100g/L.
Organic solvent in the described step (2) is oxy-compound, is selected from ethanol, Virahol, ethylene glycol, glycerol, the polyoxyethylene glycol one or more.
Trivalent iron salt in the described step (2) is iron(ic) chloride, ferric sulfate or iron nitrate.
Divalent iron salt in the described step (2) is ferrous sulfate, Iron nitrate or iron protochloride.
Alkali lye in the described step (2) is weak caustic solution, is selected from ammoniacal liquor or hydrazine hydrate.
Hollow magnetic nanometer ball in the described step (3) is the magnetic hollow nanometer ball of superparamagnetism, can be used for sewage disposal, catalysis, magnetic fluid, microwave absorbing, pharmaceutical carrier, biological enzyme is fixed or field of biosensors.
The present invention is take the cellulose nanospheres of a large amount of carboxylic groups as template, because carboxyl institute electronegativity is larger than hydroxyl, thereby easier and positively charged iron trivalent ion and iron divalent ion generation electrostatic interaction, when obtaining larger charge capacity and less nano-scale, also can guarantee magnetic particle and Mierocrystalline cellulose nuclear mortise, through high-temperature calcination in the simple inert environments, just can obtain hollow super-paramagnetism nano ball.
Beneficial effect
(1) the easy green of manufacture craft of the present invention, do not need expensive equipment, simple to operate, temperature of reaction is low, raw materials for production are cheap to be easy to get, easily large-scale production;
(2) the prepared hollow magnetic nanometer ball of the present invention has higher superparamagnetic response, size distribution is controlled, granularity is less, particle purity high, chemical constitution is even, can be used for the fields such as sewage disposal, catalysis, magnetic fluid, microwave absorbing, pharmaceutical carrier, biological enzyme are fixed, biosensor.
Description of drawings
Fig. 1 is the magnetic hysteresis loop figure of hollow super-paramagnetism nano ball;
Fig. 2 is that hollow super-paramagnetism nano ball is used for waste water from dyestuff degradation treatment design sketch.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
2g lyocell Mierocrystalline cellulose in being the NaOH solution of 1mol/L, concentration is soaked 30min, take out in the ammonium persulfate aqueous solution of immersion 50ml1mol/L after cleaning, at 60 ℃ of lower hydrolysis 12h, through centrifugal, be washed to neutrality after, and then obtain the comparatively carboxylated cellulose nanospheres of homogeneous by classification; Above-mentioned cellulose nanospheres is distributed in the 100ml water, its solid content is 10g/L again; Add first 7ml ethanol, add successively again 0.54g FeCl
3With 0.28g FeSO
47H
2O; the ammonia soln that adds 10ml, 2.5mol/L behind the stirring 15min; behind 20 ℃ of lower reaction 1h; with magnet product is collected again; send into retort furnace after the cleaning, under nitrogen protection, 600 ℃ of calcining 30min; obtain being of a size of the hollow super-paramagnetism nano ball about 48nm, magnetic strength be 45emu/g(as shown in Figure 1).Take by weighing the 0.01g matrix material, measure the H of 5mL 30%
2O
2, join successively in the NAVY E-2BA dye solution of 4mL 400mg/L concentration, under stirring, constant speed carries out the catalyzed degradation experiment, and behind 5min, the degradation rate of NAVY E-2BA was 99.5% (as shown in Figure 2).After recycling for 5 times, its absorption property remains on more than 90%.
The 3g viscose fiber in being the NaOH solution of 1mol/L, concentration is soaked 40min, taking out and cleaning the rear 100ml of immersion concentration is in the ammonium persulfate aqueous solution of 2.5mol/L, at 90 ℃ of lower hydrolysis 16h, product through centrifugal, be washed to neutrality after, and then obtain the comparatively carboxylated cellulose nanospheres of homogeneous by classification; Above-mentioned cellulose nanospheres is distributed in the 80ml water, its solid content is 15g/L again; Add first the 3ml glycerol, add successively again 0.54g FeCl
3With 0.28g FeSO
47H
2O stirs the ammonia soln that adds 10ml, 2.5mol/L behind the 10min, behind 60 ℃ of lower reaction 5h; with magnet product is collected again, sent into retort furnace after the cleaning, under nitrogen protection; 800 ℃ of calcining 30min obtain being of a size of the hollow super-paramagnetism nano ball about 61nm, and magnetic strength is 48emu/g.Take by weighing the 0.02g matrix material, join successively in the copper ion solution of 100mL10mg/L concentration, carry out adsorption experiment under constant speed stirs, behind 60min, the adsorptive capacity of cupric ion is 63.5%.After recycling for 5 times, its absorption property remains on more than 87%.
2g lyocell fiber in being the NaOH solution of 1mol/L, concentration is soaked 60min, taking out and cleaning the rear 100ml of immersion concentration is in the potassium permanganate solution of 1mol/L, at 85 ℃ of lower hydrolysis 8h, product through centrifugal, be washed to neutrality after, and then obtain the comparatively carboxylated cellulose nanospheres of homogeneous by classification; Above-mentioned cellulose nanospheres is distributed in the 70ml water, its solid content is 15g/L again; Add first 4ml ethylene glycol, again 0.27g FeCl
3With 0.14g FeSO
47H
2O stirs the ammonia soln that adds 10ml, 2.5mol/L behind the 10min, behind the reaction 3h; with magnet product is collected again, sent into retort furnace after the cleaning, under nitrogen protection; 1000 ℃ of calcining 30min obtain being of a size of the hollow super-paramagnetism nano ball about 32nm, and magnetic strength is 38emu/g.Take by weighing the 0.1g matrix material, measure the H of 5mL 30%
2O
2, join successively in the methylene blue dye solution of 4mL 280mg/L concentration, under stirring, constant speed carries out the catalyzed degradation experiment, and behind 1h, the degradation rate of methylene blue is 80.5%.After recycling for 5 times, its absorption property remains on more than 85%.
Embodiment 4
1g modal fiber in being the NaOH solution of 1mol/L, concentration is soaked 30min, taking out and cleaning the rear 30ml of immersion concentration is in the potassium dichromate aqueous solution of 1mol/L, at 75 ℃ of lower hydrolysis 3h, product through centrifugal, be washed to neutrality after, and then obtain the comparatively carboxylated cellulose nanospheres of homogeneous by classification; Above-mentioned cellulose nanospheres is distributed in the 100ml water, its solid content is 16.6g/L again; Add first 2ml ethylene glycol, again 0.54g FeCl
3With 0.28g FeSO
47H
2O stirs the hydrazine hydrate solution that adds 10ml, 2.5mol/L behind the 40min, behind the reaction 4h; with magnet product is collected again, sent into retort furnace after the cleaning, under nitrogen protection; 400 ° of C calcining 120min obtain being of a size of the hollow super-paramagnetism nano ball about 63nm, and magnetic strength is 57emu/g.Take by weighing the 0.05g matrix material, join successively in the copper ion solution of 50mL 10mg/L concentration, carry out adsorption experiment under constant speed stirs, behind 60min, the adsorptive capacity of cupric ion is 72.3%.After recycling for 5 times, its absorption property remains on more than 92%.
Claims (10)
1. the preparation method of a hollow super-paramagnetism nano ball comprises:
(1) cellulosic material is soaked 30～60min in the NaOH of 1mol/L solution, water immerses in the oxidisability salts solution after cleaning again, and 60～90 ℃ of lower hydrolysis 8～16h obtain carboxylated cellulose nanospheres; The mass ratio of cellulosic material and oxidisability salt is 1:5～10;
(2) above-mentioned cellulose nanospheres is distributed in the water, adds organic solvent, after stirring, add successively trivalent iron salt and divalent iron salt, drip again 20～60 ℃ of lower reaction 1～5h of alkali lye, and with magnet product is collected, obtain magnetic nano composite microsphere; Organic solvent accounts for 1～7% of cumulative volume, and the mol ratio of trivalent iron salt, divalent iron salt and alkali is 2:1:1～3;
(3) in inert atmosphere, magnetic nano composite microsphere is calcined at 400 ℃～1000 ℃, obtained the hollow magnetic nanometer ball.
2. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, it is characterized in that: the cellulosic material in the described step (1) is copper ammonia fibre, viscose fiber or saponified acetate; Alkali is sodium hydroxide or potassium hydroxide; The concentration of alkaline solution is 1～5mol/L.
3. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, it is characterized in that: the oxidisability salt in the described step (1) is persulphate, permanganate or dichromate, the concentration of oxidisability salt brine solution is 1～2.5mol/L.
4. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, it is characterized in that: the persulphate in the described step (1) is ammonium persulphate; Permanganate is potassium permanganate; Dichromate is potassium bichromate.
5. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, it is characterized in that: the solid content of cellulose nanospheres in dispersion liquid in the described step (2) is 10～100g/L.
6. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, it is characterized in that: the organic solvent in the described step (2) is selected from one or more in ethanol, Virahol, ethylene glycol, glycerol, the polyoxyethylene glycol.
7. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, it is characterized in that: the trivalent iron salt in the described step (2) is iron(ic) chloride, ferric sulfate or iron nitrate.
8. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, it is characterized in that: the divalent iron salt in the described step (2) is ferrous sulfate, Iron nitrate or iron protochloride.
9. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, it is characterized in that: the alkali lye in the described step (2) is ammoniacal liquor or hydrazine hydrate.
10. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, it is characterized in that: the hollow magnetic nanometer ball in the described step (3) is the magnetic hollow nanometer ball of superparamagnetism, is used for sewage disposal, catalysis, magnetic fluid, microwave absorbing, pharmaceutical carrier, biological enzyme is fixed or field of biosensors.
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Cited By (4)
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| CN103663571A (en) * | 2013-12-24 | 2014-03-26 | 武汉理工大学 | Preparation method for superparamagnetism ferroferric oxide sub-micron hollow microsphere |
| CN105800695A (en) * | 2016-03-09 | 2016-07-27 | 国际竹藤中心 | Carbon-based magnetic composite material and preparation method thereof |
| CN106947755A (en) * | 2017-04-05 | 2017-07-14 | 牡丹江医学院 | The lipase load hollow nano-sphere of vanillic aldehyde is prepared by catalytic oxidation |
| WO2018103145A1 (en) * | 2016-12-08 | 2018-06-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Micro-porous hollow nickel oxide gas-sensitive material for selectively adsorbing formaldehyde as well as preparation and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663571A (en) * | 2013-12-24 | 2014-03-26 | 武汉理工大学 | Preparation method for superparamagnetism ferroferric oxide sub-micron hollow microsphere |
| CN105800695A (en) * | 2016-03-09 | 2016-07-27 | 国际竹藤中心 | Carbon-based magnetic composite material and preparation method thereof |
| WO2018103145A1 (en) * | 2016-12-08 | 2018-06-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Micro-porous hollow nickel oxide gas-sensitive material for selectively adsorbing formaldehyde as well as preparation and application thereof |
| CN106947755A (en) * | 2017-04-05 | 2017-07-14 | 牡丹江医学院 | The lipase load hollow nano-sphere of vanillic aldehyde is prepared by catalytic oxidation |
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