CN102976416B - Preparation method of hollow superparamagnetic nanospheres - Google Patents
Preparation method of hollow superparamagnetic nanospheres Download PDFInfo
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- CN102976416B CN102976416B CN201210513705.4A CN201210513705A CN102976416B CN 102976416 B CN102976416 B CN 102976416B CN 201210513705 A CN201210513705 A CN 201210513705A CN 102976416 B CN102976416 B CN 102976416B
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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, there is good application prospect the aspect such as biosensor at magnetic fluid, microwave absorbing, sewage disposal, catalysis, pharmaceutical carrier, biological enzyme.As Fe
30
4can be used for magnetic resonance image-forming diagnose contrast medium at biological and field of medicaments, tissue repair, immunity, magnetic targeting drug administration preparation, cell separation technology and biomolecules are solidified team etc.Properties and applications that can Z 250 is subject 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 conventionally, generally between 10～20nm, is advisable, and is so relatively conducive to be excreted safely.And as the catalyzer of nanoscale, its catalytic activity is obviously better than 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 feature such as reactant fully contacts, can utilize magnetic separation technique, easily catalyzer is separated from half homogeneous system, keep the high reactivity of catalysis realization to recycle.Research shows also to show, in the time that the diameter of inorganic magnetic material is less than 30nm, just to have had superparamagnetism.Have the magnetic particle of superparamagnetism under additional the action of a magnetic field, have stronger magnetic, can be subject to the control of externally-applied magnetic field and move, when do the used time without externally-applied magnetic field, magnetic disappears very soon, thereby 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, make it have 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, preparation magnetic Fe
3o
4nanocrystalline have the advantages such as raw material is easy to get, particle purity is high, and cost is relatively low, but the more difficult control of products obtained therefrom size distribution.The problems such as cost is high, complex process and other several method more or less exists, and products therefrom is reunited serious, and uniform particles is poor.Due to Fe
3o
4, mostly there is the problem of reuniting in the magnetic of self, restricted the performance of the physics and chemistry characteristic of Z 250 uniqueness in Liquid preparation methods.Therefore by Fe
3o
4particulate load, to suitable base material, and keeps Fe
3o
4the nano-meter characteristic of particle is very important.Preparing the method that hollow ball is conventional is exactly template, adopts the method for physics or chemistry to be adsorbed on polymer microsphere surface by ferriferrous oxide nano-particle, then obtains hollow structure by high temperature sintering.Marvin's wise man waits people (CN1528675) to utilize 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 5nm left and right, but the triblock copolymer price adopting is higher.Want easy, high yield, low cost, the hollow magnetic nanometer ball that simultaneously can produce in batches, just need to find that a kind of size is controlled, machinery is good with chemical stability, preparation process is relative simply, the abundant template of surface functional group.Mierocrystalline cellulose wide material sources, cheap, and contain a large amount of active groups, there is part Study person that magnetic nano-particle and Mierocrystalline cellulose are carried out compound, send out congruence (CN101942103A) as analogy superparamagnetism magnetic particle is joined in cellulose solution, made the cellulose magnetic microsphere that is of a size of 0.1～100 μ m by electrostatic spraying technology; Zhang Lina etc. (CN 101274985B) are taking the aqueous solution of alkali/urea or thiocarbamide as solvent, and adopting direct entrapping method to prepare magnetic cellulose microsphere particle diameter is 1～600 μ m.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 is to provide a kind of preparation method of hollow super-paramagnetism nano ball, the easy green of the method manufacture craft, does not need expensive equipment, extensive, with low cost, the easy large-scale production of 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, comprising:
(1) cellulosic material is soaked to 30～60min in the NaOH of 1mol/L solution, water immerses in oxidisability salts solution after cleaning again, is hydrolyzed 8～16h at 60～90 DEG C to 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 water, adds organic solvent, after stirring, add successively trivalent iron salt and divalent iron salt, drip again at 20～60 DEG C of alkali lye and react 1～5h, 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 DEG C～1000 DEG C, obtained hollow magnetic nanometer ball.
Cellulosic material in described step (1) is regenerated cellulose fibre, has been selected from copper ammonia fibre, viscose fiber or saponified acetate.
Oxidisability salt in described step (1) is persulphate, permanganate or dichromate, and the concentration of oxidisability salt brine solution is 1～2.5mol/L.
Persulphate in described step (1) is ammonium persulphate; Permanganate is potassium permanganate; Dichromate is potassium bichromate.
The solid content of cellulose nanospheres in described step (2) in dispersion liquid is 10～100g/L.
Organic solvent in described step (2) is oxy-compound, is selected from one or more in ethanol, Virahol, ethylene glycol, glycerol, polyoxyethylene glycol.
Trivalent iron salt in described step (2) is iron(ic) chloride, ferric sulfate or iron nitrate.
Divalent iron salt in described step (2) is ferrous sulfate, Iron nitrate or iron protochloride.
Alkali lye in described step (2) is weak caustic solution, is selected from ammoniacal liquor or hydrazine hydrate.
The magnetic hollow nanometer ball that hollow magnetic nanometer ball in described step (3) is superparamagnetism, can be used for sewage disposal, catalysis, magnetic fluid, microwave absorbing, pharmaceutical carrier, biological enzyme and fixes or field of biosensors.
The present invention is taking the cellulose nanospheres of a large amount of carboxylic groups as template, because carboxyl institute electronegativity is larger than hydroxyl, thereby more easily produce electrostatic interaction with positively charged iron trivalent ion and iron divalent ion, in obtaining larger charge capacity and less nano-scale, also can ensure magnetic particle and Mierocrystalline cellulose core mortise, through high-temperature calcination in 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 is 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.
Brief description of the 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 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 are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
In the NaOH solution that is 1mol/L in concentration by 2g lyocell Mierocrystalline cellulose, soak 30min, take out in the ammonium persulfate aqueous solution of immersion 50ml1mol/L after cleaning, at 60 DEG C, be hydrolyzed 12h, through centrifugal, be washed to after neutrality, and then obtain the comparatively carboxylated cellulose nanospheres of homogeneous by classification; Above-mentioned cellulose nanospheres is distributed in 100ml water, its solid content is 10g/L again; First add 7ml ethanol, then add successively 0.54g FeCl
3with 0.28g FeSO
47H
2o; after stirring 15min, add the ammonia soln of 10ml, 2.5mol/L; at 20 DEG C, react after 1h; with magnet, product is collected again; after cleaning, send into retort furnace, under nitrogen protection, 600 DEG C of calcining 30min; obtain being of a size of the hollow super-paramagnetism nano ball of 48nm left and right, magnetic strength be 45emu/g(as shown in Figure 1).Take 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 catalyzed degradation experiment, and after 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%.
Embodiment 2
In the NaOH solution that is 1mol/L in concentration by 3g viscose fiber, soak 40min, take out in the ammonium persulfate aqueous solution that after cleaning, immersion 100ml concentration is 2.5mol/L, at 90 DEG C, be hydrolyzed 16h, product through centrifugal, be washed to after neutrality, and then obtain the comparatively carboxylated cellulose nanospheres of homogeneous by classification; Above-mentioned cellulose nanospheres is distributed in 80ml water, its solid content is 15g/L again; First add 3ml glycerol, then add successively 0.54g FeCl
3with 0.28g FeSO
47H
2o, stirs the ammonia soln that adds 10ml, 2.5mol/L after 10min, reacts after 5h at 60 DEG C; with magnet, product is collected again, after cleaning, sent into retort furnace, under nitrogen protection; 800 DEG C of calcining 30min, obtain being of a size of the hollow super-paramagnetism nano ball about 61nm, and magnetic strength is 48emu/g.Take 0.02g matrix material, join successively in the copper ion solution of 100mL10mg/L concentration, under constant speed stirs, carry out adsorption experiment, after 60min, the adsorptive capacity of cupric ion is 63.5%.After recycling for 5 times, its absorption property remains on more than 87%.
Embodiment 3
In the NaOH solution that is 1mol/L in concentration by 2g lyocell fiber, soak 60min, take out in the potassium permanganate solution that after cleaning, immersion 100ml concentration is 1mol/L, at 85 DEG C, be hydrolyzed 8h, product through centrifugal, be washed to after neutrality, and then obtain the comparatively carboxylated cellulose nanospheres of homogeneous by classification; Above-mentioned cellulose nanospheres is distributed in 70ml water, its solid content is 15g/L again; First add 4ml ethylene glycol, then 0.27g FeCl
3with 0.14g FeSO
47H
2o, stirs the ammonia soln that adds 10ml, 2.5mol/L after 10min, after reaction 3h; with magnet, product is collected again, after cleaning, sent into retort furnace, under nitrogen protection; 1000 DEG C of calcining 30min, obtain being of a size of the hollow super-paramagnetism nano ball about 32nm, and magnetic strength is 38emu/g.Take 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 catalyzed degradation experiment, and after 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
In the NaOH solution that is 1mol/L in concentration by 1g modal fiber, soak 30min, take out in the potassium dichromate aqueous solution that after cleaning, immersion 30ml concentration is 1mol/L, at 75 DEG C, be hydrolyzed 3h, product through centrifugal, be washed to after neutrality, and then obtain the comparatively carboxylated cellulose nanospheres of homogeneous by classification; Above-mentioned cellulose nanospheres is distributed in 100ml water, its solid content is 16.6g/L again; First add 2ml ethylene glycol, then 0.54g FeCl
3with 0.28g FeSO
47H
2o, stirs the hydrazine hydrate solution that adds 10ml, 2.5mol/L after 40min, after reaction 4h; with magnet, product is collected again, after cleaning, sent into retort furnace, 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 0.05g matrix material, join successively in the copper ion solution of 50mL 10mg/L concentration, under constant speed stirs, carry out adsorption experiment, after 60min, the adsorptive capacity of cupric ion is 72.3%.After recycling for 5 times, its absorption property remains on more than 92%.
Claims (7)
1. a preparation method for hollow super-paramagnetism nano ball, comprising:
(1) cellulosic material is soaked to 30～60min in the NaOH of 1mol/L solution, water immerses in oxidisability salts solution after cleaning again, is hydrolyzed 8～16h at 60～90 DEG C to obtain carboxylated cellulose nanospheres; The mass ratio of cellulosic material and oxidisability salt is 1:5～10; Wherein cellulosic material is copper ammonia fibre, viscose fiber or saponified acetate; Oxidisability salt is persulphate, permanganate or dichromate;
(2) above-mentioned carboxylated cellulose nanospheres is distributed in water, adds organic solvent, after stirring, add successively trivalent iron salt and divalent iron salt, then drip alkali lye, react 1～5h at 20～60 DEG C, 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; Wherein organic solvent is selected from one or more in ethanol, Virahol, ethylene glycol, glycerol, polyoxyethylene glycol; Alkali lye is ammoniacal liquor or hydrazine hydrate;
(3) in inert atmosphere, magnetic nano composite microsphere is calcined at 400 DEG C～1000 DEG C, obtained hollow magnetic nanometer ball.
2. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, is characterized in that: the concentration of the oxidisability salt brine solution in described step (1) is 1～2.5mol/L.
3. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, is characterized in that: the persulphate in described step (1) is ammonium persulphate; Permanganate is potassium permanganate; Dichromate is potassium bichromate.
4. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, is characterized in that: the solid content of the carboxylated cellulose nanospheres in described step (2) in dispersion liquid is 10～100g/L.
5. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, is characterized in that: the trivalent iron salt in described step (2) is iron(ic) chloride, ferric sulfate or iron nitrate.
6. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, is characterized in that: the divalent iron salt in described step (2) is ferrous sulfate, Iron nitrate or iron protochloride.
7. the preparation method of a kind of hollow super-paramagnetism nano ball according to claim 1, it is characterized in that: the magnetic hollow nanometer ball that the hollow magnetic nanometer ball in described step (3) is superparamagnetism, fix or field of biosensors for sewage disposal, catalysis, magnetic fluid, microwave absorbing, pharmaceutical carrier, biological enzyme.
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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 |
| CN106587173B (en) * | 2016-12-08 | 2019-01-01 | 上海纳米技术及应用国家工程研究中心有限公司 | It is a kind of for the micro porous hollow nickel oxide gas sensing materials and device of formaldehyde selective absorption and preparation and application |
| 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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