CN100485833C - Method for synthesizing magnetic metallic oxide nano wire with high length-diameter ratio - Google Patents
Method for synthesizing magnetic metallic oxide nano wire with high length-diameter ratio Download PDFInfo
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- CN100485833C CN100485833C CNB2004100096814A CN200410009681A CN100485833C CN 100485833 C CN100485833 C CN 100485833C CN B2004100096814 A CNB2004100096814 A CN B2004100096814A CN 200410009681 A CN200410009681 A CN 200410009681A CN 100485833 C CN100485833 C CN 100485833C
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Abstract
Through wet chemical method, the invention prepares one-dimensional Nano material of magnetic metallic oxide; especially, the invention is related to composite system of polyalcohol. In water solution of hydrophilic high polymer, using synthesis under metallic ion coprecipitation method obtains Nano wire of magnetic metallic oxide with high length-diameter ratio and even diameter. Adjusting scale among components of polyalcohol and speed for adding components can control length-diameter ratio of Nano wire of magnetic metallic oxide.
Description
Technical field
The invention belongs to the technical field for preparing the one-dimensional magnetic metal oxide nano-material with wet chemical method, particularly synthetic method in compound how pure system with magnetic metal oxide nano wire of high length-diameter ratio.
Background technology
Recently, one-dimensional nano structure material such as line, rod, band, pipe etc. are becoming the focus of scientific and technical personnel's research gradually.Because one-dimensional nano structure material has unique mesoscopic physics and chemical property (these all are that macroscopic material does not possess fully), thereby they have potential application on the assemble nanometer device.Monodimension nanometer material can provide good research system on functions such as electric heating transmission, they can be used for nanoscale devices such as preparation electricity, photoelectricity, electrochemistry and motor.The one-dimensional magnetic nano material is subjected to people's special concern equally because of its significant characteristic.As the attractive part of arranging the magnetic Nano rod is that it can be used for magnetic perpendicular recording material.Studies show that magnetic nanometer also has special purpose at biomedical sector, it is more taller than magnetic nanoparticle to discover that particularly employing magnetic nickel nano line separates mammiferous cell (as the mouse fibroblast).This is to have very strong anisotropy because of the high length-diameter ratio of magnetic nanometer, makes it have bigger remanent magnetism under downfield, and super paramagnetic particle does not then have remanent magnetism fully.
At present, preparation one-dimensional magnetic nano material is becoming a focus of nanochemistry.But the method for preparing this material now also is not a lot.As Tanase people such as (U.S.) at " applicating physical magazine " (Journal Application Physics, volume was the 8549th page in 2002 91) go up to adopt anodised aluminium to do hard template to be a kind of effectively electro-deposition method, can to prepare magnetic metal and alloy.But the nano wire that this method is synthetic is owing to be subjected to the restriction of stencil structure, and its draw ratio is not high, and diameter is also relatively thicker, and can only produce the nano wire of polycrystalline.In addition.Ge people such as (China) is at " applicating physical magazine " (Journalof Application Physics, calendar year 2001s 90 the 509th page of volume) go up soft template methods such as adopting lecithin, and Sudakar people such as (India) is at " materials chemistry magazine " (Journal of MaterialChemistry, volume was the 107th page in 2002 the 12nd) adopt oxide-reduction method to form elongated piece easily, and also the template composition also is difficult to remove.Kyoungja people such as (Japan) adopts the inverse micelle method of oleic acid protection to synthesize γ-Fe
2O
3Nanometer rods though the draw ratio of this material is relevant with the ratio of oleic acid/water, but still can not synthesize the very big nano material of draw ratio (Adv.Mater.2003,15 (20), 1761) " advanced material ".
Summary of the invention
A purpose of the present invention provides a kind of synthetic method of magnetic metal oxide nano wire.
A further object of the present invention provides a kind of high length-diameter ratio that has, and the synthetic method of the uniform one-dimensional magnetic metal oxide nano-wire of diameter, can effectively control the diameter and the draw ratio of nano wire with this method.
The objective of the invention is to be achieved through the following technical solutions:
Adopt wet chemical method, in the aqueous solution of hydrophilic high molecular polymer, obtain high length-diameter ratio and the even magnetic metal oxide nano wire of diameter by the metal ion coprecipitation method; Can control the draw ratio of magnetic metal oxide nano wire by regulating ratio and interpolation speed between many alkoxide components, its maximum draw ratio can reach 500.
Hydrophilic high molecular polymer is dissolved in the solvent, adds enough water and mix; Add low mass molecule alcohol and alkali then, stir, obtain compound how pure system, wherein, the part by weight of hydrophilic high molecular polymer and low mass molecule alcohol is 0.1～0.5, and the preferred weight ratio is 0.25～0.5; The concentration of alkali in compound how pure system is 0.02～0.08mol/L, and preferred concentration is 0.02～0.06mol/L.In system, feed nitrogen or inert gas deoxygenation about half an hour after, after system is warming up to 70～120 ℃ of reaction temperatures, preferred temperature is 80～100 ℃, presses the mixed solution that certain speed adds divalent metal salt and trivalent iron salt, and wherein the concentration of bivalent metal ion is 1～4 * 10 in the system
-3Mol/L, the concentration of trivalent Fe ion is 2～8 * 10
-3Mol/L, the mol ratio of two kinds of ions is 1:2, and interpolation speed is 1.5～5ml/ minute, and preferably interpolation speed is 1.5～2.5ml/ minute.Successive reaction stops reaction after a few hours.After system is reduced to room temperature, precipitate and separate under magnetic field, with the deionized water cyclic washing repeatedly after, about 60 ℃ dry 12 hours down, obtain the magnetic metal oxide nano wire of one dimension high length-diameter ratio, diameter is 10～30 nanometers, draw ratio 10～500.
Described hydrophilic high molecular polymer comprises polyvinyl alcohol (PVA), polyethylene glycol (PEG) or poly-(oxireme-epoxy third rare-oxireme) triblock copolymer (P123) etc.
Described solvent also can dissolve any solvent of hydrophilic high mol for dissolving each other with water, wherein is preferably water, methyl alcohol, ethanol or isopropyl alcohol etc.
Described low mass molecule alcohol comprises ethanol, ethylene glycol, propylene glycol, diglycol, triethylene-glycol etc.
Described alkali comprises organic and inorganic base, as NaOH, KOH, NH
3H
2O, urea, HMTA (hexamethylenetetramine) or the like wherein are preferably hexamethylenetetramine; The concentration of alkali is 0.02～0.08mol/L, and the concentration of preferred bases is 0.02～0.06mol/L.
Described inert gas comprises helium or argon gas etc.
Described divalent metal salt comprises: divalent iron salt such as frerrous chloride, ferrous sulfate or ferrous acetate etc.; The zinc salt of divalence such as zinc sulfate, zinc chloride, zinc nitrate or zinc acetate etc.; Divalent cobalt such as cobaltous sulfate, cobalt chloride, cobalt nitrate or cobalt acetate etc.; The manganese salt of divalence such as manganese sulfate, magnesium chloride or manganese nitrate etc.; The nickel salt of divalence such as nickel chloride, nickelous sulfate or nickel nitrate etc.; The mantoquita of divalence such as copper sulphate, copper nitrate, copper chloride or Schweinfurt green etc.; The magnesium salts of divalence such as magnesium sulfate, magnesium chloride or magnesium nitrate etc., described divalent metal salt can be one or more the mixtures in the above-mentioned salt.
Described trivalent iron salt comprises ferric sulfate, ferric nitrate or iron chloride etc.
In one dimension ferric oxide nano wire forming proces; low mass molecule alcohol class such as ethylene glycol play important effect at its nucleation stage; thereby the hydroxyl that it had can form protective layer at nucleating surface with the metallic ion coordination of nucleating surface, has limited it and has further assembled and growth.Hydrophilic macromolecule has then played the effect of induced growth.Owing to have a large amount of hydroxyls on the hydrophilic macromolecule chain, they equally can with the metallic ion coordination of nucleating surface.Because the surface energy difference of different crystal faces, so its speed of growth difference.Experimental result shows, because the coordination of hydroxyl makes crystal obviously fast than the growth rate along other crystal face along the growth rate of (311) crystal face on the hydrophilic macromolecule, and the chain structure of polymer makes the easier formation linear structure of crystal.Therefore, select suitable hydrophilic high mol concentration and with the low mass molecule alcohol proper proportion, can obtain the very high one-dimensional magnetic metal oxide nano-wire of draw ratio.In the present invention, the concentration of suitable hydrophilic high mol is 1～20wt%, and preferred concentration is 5～20wt%, and preferred concentration is 10～20wt%.
The kind of alkali and consumption are to influence the important factor that one-dimensional material forms.Different precipitation reagents may influence the final pattern of product.Because the alkalescence of inorganic base is too strong, reaction speed is too fast, and the product great majority that obtain are graininess, is mingled with a small amount of low draw ratio product, needs just can obtain one-dimensional nano line through separating.Therefore suitable precipitation reagent is can slowly decompose the compound that obtains alkaline matter along with temperature raises in system, preferred suitable precipitation reagent is selected the organic base of pyrolytic among the present invention, comprise hexamethylenetetramine, urea etc. wherein are preferably hexamethylenetetramine.Reaction temperature is the key factor that influences reaction speed and crystal composition, and the suitable reactions temperature is 70～120 ℃, and preferred temperature is 80～100 ℃.
Method of the present invention has versatility, can be used to prepare multiple metal oxide nano-wire.
Raw material used in the present invention and preparation method's process all do not have harmful effect to environment, and method of the present invention time-saving and efficiency is simple, are easy to apply, and can effectively control the diameter and the draw ratio of nano wire.
Magnetic nano wire of the present invention is of many uses, is widely used in bio-separation, Wave suction composite material field.
Description of drawings
Fig. 1. the stereoscan photograph of the embodiment of the invention 1 magnetic ferric oxide nano line.
Fig. 2. the partial enlarged drawing of Fig. 1.
Embodiment
Embodiment 1
The P123 alcoholic solution of 10ml added in 250 ml waters mix; Add ethylene glycol, the 1g hexamethylenetetramine of 5ml then, stir; Feed the nitrogen deoxygenation, be warming up to 80 ℃ after, press certain speed adding FeCl
2And FeCl
3Mixed solution, Fe in the system wherein
2+The concentration of ion is 1～4 * 10
-3Mol/L, Fe
3+The concentration of ion is 2～8 * 10
-3Mol/L, interpolation speed 1.7～2.5ml/ minute, the mol ratio of two kinds of ions are 1:2, and successive reaction stops reaction after a few hours, and temperature is reduced to room temperature.Under magnetic field behind the precipitation separating, washing 60 ℃ dry 12 hours down, the line number of going forward side by side time is to separate purification one-dimensional material particle.Product neutral line structure proportion is higher than 70%, and nanowire diameter is 10～15 nanometers, and maximum draw ratio can reach 500.
Embodiment 2
The PEG aqueous solution of 20ml added in 250 ml waters mix; Add ethylene glycol, the 2g hexamethylenetetramine of 10ml then, stir; Feed the nitrogen deoxygenation, be warming up to 80 ℃ after, press certain speed adding FeSO
4And FeCl
3Mixed solution, Fe in the system wherein
2+The concentration of ion is 1～4 * 10
-3Mol/L, Fe
3+The concentration of ion is 2～8 * 10
-3Mol/L, the mol ratio of two kinds of ions is 1:2, interpolation speed 2.5～4ml/ minute, successive reaction stopped reaction and reduce to room temperature after a few hours.Under magnetic field behind the precipitation separating, washing 60 ℃ dry 12 hours down, the line number of going forward side by side time is to separate purification one-dimensional material particle.The gained nanowire diameter is 20～30 nanometers, draw ratio 50～300.
Embodiment 3:
The PVA aqueous solution of 20ml added in 250 ml waters mix; The ethylene glycol that adds 20ml then, the 3g hexamethylenetetramine stirs; Logical as the nitrogen deoxygenation, be warming up to 80 ℃ after, press certain speed adding manganese nitrate, mixed solution (the mol ratio Mn of frerrous chloride and iron chloride
2+: Fe
2+: Fe
3+=1:1:: 4), wherein the concentration of bivalent metal ion is 2～4 * 10 in the system
-3Mol/L, the concentration of trivalent Fe ion is 4～8 * 10
-3Mol/L, interpolation speed 1.2～1.7ml/ minute, successive reaction stopped reaction and reduce to room temperature after a few hours.Under magnetic field behind the separating, washing 60 ℃ dry 12 hours down, the line number of going forward side by side time proposes the one-dimensional material particle to separate.The gained nanowire diameter is 20～30 nanometers, and draw ratio is 10～150.
Embodiment 4
The PEG aqueous solution of 40ml added in 250 ml waters mix; Add ethylene glycol, the 4g urea of 50ml then, stir; Feed the nitrogen deoxygenation, be warming up to 80 ℃ after, press certain speed adding CoCl
2And FeCl
3Mixed solution (mol ratio Co
2+: Fe
3+=1:2), Co in the system wherein
2+The concentration of ion is 1～4 * 10
-3Mol/L, Fe
3+The concentration of ion is 2～8 * 10
-3Mol/L, interpolation speed 2.5～4ml/ minute, successive reaction stopped reaction and reduce to room temperature after a few hours.Under magnetic field behind the precipitation separating, washing 60 ℃ dry 12 hours down, the line number of going forward side by side time is to separate purification one-dimensional material particle.The gained nanowire diameter is 15～30 nanometers, draw ratio 50～100.
Embodiment 5
The P123 aqueous solution of 10ml added in 250 ml waters mix; Add ethylene glycol, the 4.5g urea of 10ml then, stir; Feed the nitrogen deoxygenation, be warming up to 80 ℃ after, press a certain proportion of ZnAc of certain speed adding
2And FeCl
3Mixed solution (mol ratio Zn
2+: Fe
3+=1:2), Zn in the system wherein
2+The concentration of ion is 1～4 * 10
-3Mol/L, Fe
3+The concentration of ion is 2～8 * 10
-3Mol/L, interpolation speed 2.5～5ml/ minute.Successive reaction stopped reaction and reduces to room temperature after a few hours.Under magnetic field behind the precipitation separating, washing 60 ℃ dry 12 hours down, the line number of going forward side by side time is to separate purification one-dimensional material particle.The gained nanowire diameter is 20～30 nanometers, draw ratio 100～300.
Embodiment 6
The PEG aqueous solution of 20ml added in 250 ml waters mix; Add ethylene glycol, the 10ml ammoniacal liquor of 10ml then, stir; Feed the nitrogen deoxygenation, be warming up to 80 ℃ after, add a certain proportion of NiCl by certain speed
2And Fe (NO
3)
3Mixed solution (mol ratio Ni
2+: Fe
3+=1:2), Ni in the system wherein
2+The concentration of ion is 1～4 * 10
-3Mol/L, Fe
3+The concentration of ion is 2～8 * 10
-3Mol/L, interpolation speed 2.5～4ml/ minute, successive reaction stopped reaction and reduce to room temperature after a few hours.Under magnetic field behind the precipitation separating, washing 60 ℃ dry 12 hours down, the line number of going forward side by side time is to separate purification one-dimensional material particle.The gained nanowire diameter is 10～30 nanometers, draw ratio 50～100.
Embodiment 7
The PEG aqueous solution of 15ml added in 250 ml waters mix; Add ethylene glycol, the 5ml sodium hydrate aqueous solution of 20ml then, stir; Feed the nitrogen deoxygenation, be warming up to 80 ℃ after, add a certain proportion of CuSO by certain speed
4And FeCl
3Mixed solution (mol ratio Fe
2+: Fe
3+=1:2), Cu in the system wherein
2+The concentration of ion is 1～4 * 10
-3Mol/L, Fe
3+The concentration of ion is 2～8 * 10
-3Mol/L, interpolation speed 2.5～4ml/ minute, successive reaction stopped reaction and reduce to room temperature after a few hours.Under magnetic field behind the precipitation separating, washing 60 ℃ dry 12 hours down, the line number of going forward side by side time is to separate purification one-dimensional material particle.The gained nanowire diameter is 20～30 nanometers, draw ratio 20～150.
Claims (8)
1. the synthetic method with magnetic metal oxide nano wire of high length-diameter ratio is characterized in that: hydrophilic high molecular polymer is dissolved in the solvent, adds entry and mix; Add low mass molecule alcohol and alkali then, stir, obtain compound how pure system, wherein, the part by weight of hydrophilic high molecular polymer and low mass molecule alcohol is 0.1～0.5, and the concentration of alkali in compound how pure system is 0.02～0.08mol/L; System is warming up to 70～120 ℃ of reaction temperatures after feeding nitrogen or inert gas deoxygenation, add the mixed solution of divalent metal salt and trivalent iron salt, and wherein the concentration of bivalent metal ion is 1～4 * 10 in the system
-3Mol/L, the concentration of ferric ion is 2～8 * 10
-3Mol/L; Reaction is to finishing, cooling, and precipitate and separate under magnetic field, washing, drying obtains the one dimension draw ratio and is the magnetic metal oxide nano wire of 10～500 high length-diameter ratio;
Described hydrophilic high molecular polymer is polyvinyl alcohol, polyethylene glycol or poly-(oxireme-epoxy third rare-oxireme) triblock copolymer;
Described low mass molecule alcohol is ethanol, ethylene glycol, propylene glycol, diglycol or triethylene-glycol.
2. method according to claim 1 is characterized in that: the diameter of the magnetic metal oxide nano wire of described one dimension high length-diameter ratio is 10～30 nanometers.
3. method according to claim 1 is characterized in that: the speed of the mixed solution of described adding divalent metal salt and trivalent iron salt is 1.5～5ml/ minute.
4. method according to claim 1 is characterized in that: described alkali is NaOH, potassium hydroxide, ammoniacal liquor, urea or hexamethylenetetramine.
5. according to claim 1 or 4 described methods, it is characterized in that: the concentration of described alkali is 0.02～0.06mol/L.
6. method according to claim 1 is characterized in that: described inert gas is helium or argon gas.
7. according to claim 1 or 3 described methods, it is characterized in that: described divalent metal salt is selected from one or more the mixture in frerrous chloride, ferrous sulfate, ferrous acetate, zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt acetate, manganese sulfate, magnesium chloride, manganese nitrate, nickel chloride, nickelous sulfate, nickel nitrate, copper sulphate, copper nitrate, copper chloride, Schweinfurt green, magnesium sulfate, magnesium chloride, the magnesium nitrate.
8. according to claim 1 or 3 described methods, it is characterized in that: described trivalent iron salt is ferric sulfate, ferric nitrate or iron chloride.
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| CN100485833C true CN100485833C (en) | 2009-05-06 |
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| CN100417751C (en) * | 2007-02-07 | 2008-09-10 | 天津大学 | Preparation method of ferromagnetic nano wire |
| WO2011031483A2 (en) * | 2009-08-25 | 2011-03-17 | Cambrios Technologies Corporation | Methods for controlling metal nanostructures morphology |
| CN104072782B (en) * | 2014-07-03 | 2016-09-14 | 江苏大学 | A kind of preparation method of magnetic poly phosphazene nano wire |
| CN105777095A (en) * | 2016-03-09 | 2016-07-20 | 苏州特瓦储能科技有限公司 | Preparation method of ferrite nano material and ferrite nano material prepared with method |
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| CN1397932A (en) * | 2002-07-29 | 2003-02-19 | 南京大学 | Fe-Co alloy nanoline array as high-density magnetic perpendicualr recording material and its preparing process |
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