CN101337279B - Preparation and separation method of monodisperse amorphous state nickel nano particle - Google Patents
Preparation and separation method of monodisperse amorphous state nickel nano particle Download PDFInfo
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- CN101337279B CN101337279B CN2008101181704A CN200810118170A CN101337279B CN 101337279 B CN101337279 B CN 101337279B CN 2008101181704 A CN2008101181704 A CN 2008101181704A CN 200810118170 A CN200810118170 A CN 200810118170A CN 101337279 B CN101337279 B CN 101337279B
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Abstract
A method for preparing and separating monodisperse superparamagnetic iron nanoparticles that can be completely dissolved in polar and non-polar organic solvents comprises the following steps: taking iron acetylacetonate as a raw material; taking whiteruss as a reaction medium; taking trioctyl phosphine and oleylamine as stabilizing agents (or: protective solutes, surface modifying agents); taking an organic ferric compound as a catalyzer; taking polylol as a morphological modifying agent; mixing the above substances in a kettle-type reactor according to a certain ratio; heating the substances with hydrogen to the reaction temperature (150 to 350 DEG C); reacting for 3 hours; obtaining iron nanoparticles of good crystallinity; and adopting an external applied magnetic field to assist the solvent fractionating method, so as to separate the iron nanoparticles from the reaction system. The powdery iron nanoparticles can once again disperse into organic solvents such as chloroform, sherwood oil, etc. without sedimentation.
Description
Technical field
The present invention relates to a kind of preparation and separation method of monodisperse amorphous state nickel nano particle, and it is to belong to the preparation of magnetic Nano yardstick material and the improvement and the innovation of separation method.Prepared monodisperse amorphous state nickel nano particle can be dissolved in polarity and the non-polar organic solvent fully.
Background technology
Magnetic nano-particle is the important component part of nanoscale material.The element that has magnetic under the normal temperature has only iron, cobalt, nickel, and wherein iron has maximum saturation magnetization.And iron is the maximum metallic element of occurring in nature content, and therefore preparing the pure iron nano particle not only has important theory to be worth, and has more application prospects.Because iron is comparatively active transition metal, the ferrite of nanoscale is more stable, so the report of relevant pure iron nano particle is actually rare in the document.Only method has following several: (1) is raw material with the carbonyl iron, thermal decomposition or ultrasonic decomposition method in ether solvent; (2) molysite or ferrite reducing process; (3) vapour deposition process; (4) physical grinding, shearing method.From images of transmissive electron microscope, only there is the nano particle pattern of first method preparation better not have coalescence.The nano particle coalescence of its excess-three kind method preparation is very serious.
There is following defective in the preparation method who with the carbonyl iron is raw material: (1) carbonyl iron is poisonous, and decomposition temperature is low, store and transportation very inconvenient.Carbonyl iron also is simultaneously the specially goods and materials of control of country, though domestic have production, but is mainly used in military enterprise, does not have domestic reagent to sell at present on the market.And buy external reagent, then cost an arm and a leg; (2) reaction medium adopts the expensive organic ethers reagent of higher boiling, for example: octyl ether, diphenyl ether etc.; (3) gained nano particle diameter scope is distributed more widely, expect that monodisperse nanoparticle also needs further nano particle to be screened.Therefore this method only is fit to laboratory research, and unsuitable large-scale industrial production.
Summary of the invention
Preparation and separation method that purpose of the present invention has proposed a kind of monodisperse amorphous state nickel nano particle with regard to being to avoid the deficiencies in the prior art part.This method is the reagent that replaces costliness in the existing method with the raw material of cheapness, as the chemosynthesis reaction device, synthesizes the monodisperse iron nano particle with superparamagnetism with stainless steel autoclave; As) with this nano particle as the nuclei of crystallization, can prepare other magnetic core-shell structure nanometer particles; As the pure iron nano particle is dissolved in organic solvent, can be used as magnetic fluid and use; Also available this pure iron nano particle purifies the drinking water source of organochlorine contamination; Also can be at biochemical field Fe nanometer particles isolated protein.
The present invention is to be raw material with the ferric acetyl acetonade, successfully synthesizes single pure iron nano particle that disperses under hydrogen and stabilizing agent existence condition.Reaction equation is as follows:
The effect of hydrogen is that be zero fe with oxidation number for+3 iron is reduced to oxidation number.Because the surface of nanometer iron can be very high, so the stabilizing agent molecule can be adsorbed on the nanometer iron surface, the surface that has so not only reduced nanometer iron can, stop the Fe nanometer particles coalescence and grow up into block materials, and can also the occluded oxygen molecule, hydrone etc. contacts with the nanometer iron surface, makes the Fe nanometer particles can stable existence.Observe from high-resolution-ration transmission electric-lens,,, also can observe the existence of lattice, but belong to irregular shape though Fe nanometer particles does not have coalescence if there is not the existence of pattern dressing agent.Have under the condition of pattern dressing agent existence, Fe nanometer particles is spherical in shape substantially, and particle size distribution range is very narrow, and standard deviation is 3.5%.Usually the particle diameter distribution standard deviation can be thought monodisperse nanoparticle less than 5%.
The prepared monodisperse amorphous state nickel nano particle of method of the present invention can be dissolved in polarity and the non-polar organic solvent fully.This method is implemented by following steps, that is:
With the ferric acetyl acetonade is raw material, and atoleine is a reaction medium, and tri octyl phosphine and oleyl amine are stabilizing agent (or claiming protective agent, coating material), and polyalcohol is the pattern dressing agent.In tank reactor, above-mentioned substance is mixed, feed hydrogen, be warming up to 200-300 ℃ then, reacted 2-5 hour.Treat that kettle is cooled to room temperature, take out reactant liquor and put into beaker, add ethanol and benzinum by a certain percentage, leave standstill after fully stirring; Beaker is placed on forever on the strong magnet, and can observe the liquid layering this moment.Remove supernatant liquor, repeat above-mentioned steps, be enriched in beaker bottom until the black powder.Powder is placed vacuum drying chamber, and under 100 ℃ and 1 millimetres of mercury condition dry 1 hour, the cooling back was taken out nano particle and is placed storage nitrogen protection under.
In entire reaction course, each composition is as follows:
(1) raw materials used: ferric acetyl acetonade;
(2) nano particle stabilizing agent (claiming again: protective agent, coating material etc.):
A organic phosphine: tri octyl phosphine, tributylphosphine, tricresyl phosphite monooctyl ester etc.;
B organic amine: oleyl amine, octylame etc.;
C carboxylic acid: oleic acid, sad etc.;
D polymer: polyvinyl alcohol
(3) nano particle pattern dressing agent: polyalcohol (for example: sorbierite, 1,2-12 glycol, 1,2-16 glycol, polyvinyl alcohol etc.)
(4) reaction medium: atoleine, oleic acid, diphenyl ether, dioctyl ether
The gained nano particle turns out to be pure iron through X-ray diffraction analysis (XRD); Transmission electron microscope analysis, Fe nanometer particles is spherical in shape, and average grain diameter is 11.5 nanometers, particle diameter distribution standard deviation σ=3.5%; The superconductive quantum interference magnetometric analysis shows that the magnetic resistance of Fe nanometer particles was zero when specific saturation magnetization was 121emu/g25 ℃, had superparamagnetism.
The specific embodiment
Come enumeration technical characterstic of the present invention below in conjunction with drawings and Examples.
In actual fabrication, be the method for the present invention that realizes like this in the laboratory:
Raw material, nano particle stabilizing agent, nano particle pattern dressing agent, reaction medium are packed in the stainless steel autoclave formula reactor, feed the high pure nitrogen deoxygenation.In autoclave, feed hydrogen (purity 99.9%), be warming up to reaction temperature then, reacted 2-5 hour.
After reaction finished, water made the cooling of reaction kettle body chilling.Lentamente reacting kettle inner pressure is reduced to normal pressure, open reactor, liquid is black in the still.Take out reaction liquid and put into beaker.Not precipitation of reactor bottom can be found in observing response device bottom.
In beaker, add a certain proportion of ethanol and benzinum (1～10: 1,60-90 ℃), after fully stirring beaker is rested on strong magnet (magnetic field intensity 1.2 teslas) surface forever.Liquid in the beaker is divided into two-layer up and down.The ethanol on upper strata not only has benzinum in mutually and exists, and is existed by the extract paraffin body on a small quantity in addition.The atoleine of lower floor not only contains a spot of benzinum in mutually, also contains nano particle, and just the amount of atoleine reduces relatively.Repeat so several times, just can whole atoleine extractings be finished.Final whole nano particle all is deposited on beaker bottom.Because nano particle is insoluble to ethanol, can wash nano particle 2-3 time with small amount of ethanol again this moment, to remove nano particle unnecessary organic molecule on every side, the nano particle that will mix small amount of ethanol then is placed in the vacuum drying chamber following dry one hour in 100 ℃.Take out the cooling back, can obtain the powder of nano particle.After this nano particle powder weighed, the black powder that takes a morsel added in benzinum or the chloroform, and powder is dissolved in the organic solvent rapidly.Can observe the pattern, the particle diameter that are dissolved in the low boiling point organic solvent magnetic nano-particle by transmission electron microscope and high-resolution-ration transmission electric-lens distributes and lattice.Remaining nano particle powder can be used to do X-ray diffraction analysis and magnetometric analysis.
With 1 of 2mmol ferric acetyl acetonade, 6ml tri octyl phosphine, 6ml oleyl amine, 2mmol, 2-16 glycol, 40ml atoleine are packed in the 100ml stainless steel autoclave formula reactor, feed the high pure nitrogen deoxygenation.Feed hydrogen (purity 99.9%) in autoclave, pressure is charged to 4.0MPa, and mixing speed is adjusted to 500rpm, is warming up to 300 ℃ then, reacts 3 hours.After reaction finishes, open reactor, take out reactant liquor and place 250 ml beakers.In beaker, add 40 milliliters of ethanol and 10 milliliters of benzinums (60-90 ℃), be statically placed in strong magnet surface forever after fully stirring.Liquid in the beaker will be divided into two-layer, remove and remove supernatant liquor.Repeat above-mentioned steps 3-5 time, the black nano particle will be enriched in beaker bottom.100 ℃ of vacuum drying one hour, cooling can obtain the nano particle powder then with the gained nano particle.Get 2 milligrams of nano particles and be dissolved in 5 milliliters of benzinums (60-90 ℃), this fluid drips on ultrathin carbon films, is adopted low pattern and the lattice of differentiating transmission electron microscope and high-resolution-ration transmission electric-lens observation nano particle respectively, the result as shown in Figure 1 and Figure 2.The gained nano particle is spherical, average grain diameter 11.5 nanometers, particle diameter distribution standard deviation σ=3.5%.Solid sample is done X-ray diffraction analysis and magnetometric analysis, and the result as shown in Figure 3, Figure 4.The gained nano particle turns out to be pure iron through X-ray diffraction analysis (XRD); The superconductive quantum interference magnetometric analysis shows that specific saturation magnetization is 121emu/g in the time of 25 ℃, and the magnetic resistance of Fe nanometer particles is zero, has superparamagnetism.
2mmol ferric acetyl acetonade, 2ml tri octyl phosphine, 3ml oleyl amine, 40ml atoleine are packed in the 100ml stainless steel autoclave formula reactor, feed the high pure nitrogen deoxygenation.Feed hydrogen (purity 99.9%) in autoclave, pressure is charged to 4.0MPa, and mixing speed is adjusted to 500rpm, is warming up to 300 ℃ then, reacts 5 hours.After reaction finishes, open reactor, take out reactant liquor and place 250 ml beakers.In beaker, add 40 milliliters of ethanol and 10 milliliters of benzinums (60-90 ℃), be statically placed in strong magnet surface forever after fully stirring.Liquid in the beaker will be divided into two-layer, remove and remove supernatant liquor.Repeat above-mentioned steps 3-5 time, the black nano particle will be enriched in beaker bottom.100 ℃ of vacuum drying one hour, cooling can obtain the nano particle powder then with the gained nano particle.Get 2 milligrams of nano particles and be dissolved in 5 milliliters of benzinums (60-90 ℃), this fluid drips on ultrathin carbon films, is adopted low pattern and the lattice of differentiating transmission electron microscope and high-resolution-ration transmission electric-lens observation nano particle respectively, result such as Fig. 5, shown in Figure 6.The gained nano particle is irregular nanocrystal.Solid sample is done X-ray diffraction analysis, and the result as shown in Figure 7.The gained nano particle turns out to be pure iron through X-ray diffraction analysis (XRD).
Embodiment 3
2mmol ferric acetyl acetonade, 2ml tri octyl phosphine, 3ml oleyl amine, 40ml atoleine are packed in the 100ml stainless steel autoclave formula reactor, feed the high pure nitrogen deoxygenation.Feed high pure nitrogen (purity 99.99%) in autoclave, pressure is charged to 4.0MPa, and mixing speed is adjusted to 500rpm, is warming up to 300 ℃ then, reacts 5 hours.After reaction finishes, open reactor, take out reactant liquor and place 250 ml beakers.In beaker, add 40 milliliters of ethanol and 10 milliliters of benzinums (60-90 ℃), be statically placed in strong magnet surface forever after fully stirring.Liquid in the beaker will be divided into two-layer, remove and remove supernatant liquor.Repeat above-mentioned steps 3-5 time, the black nano particle will be enriched in beaker bottom.100 ℃ of vacuum drying one hour, cooling can obtain the nano particle powder then with the gained nano particle.Get 2 milligrams of nano particles and be dissolved in 5 milliliters of benzinums (60-90 ℃), this fluid drips on ultrathin carbon films, is adopted low pattern and the lattice of differentiating transmission electron microscope and high-resolution-ration transmission electric-lens observation nano particle respectively, result such as Fig. 8, shown in Figure 9.The gained nano particle is the ball shaped nano crystal, average grain diameter 12.6 nanometers.Solid sample is done X-ray diffraction analysis and magnetometric analysis, result such as Figure 10, shown in Figure 11.The gained nano particle turns out to be tri-iron tetroxide through X-ray diffraction analysis (XRD).The superconductive quantum interference magnetometric analysis shows that specific saturation magnetization is 65emu/g in the time of 25 ℃, and the magnetic resistance of ferriferrous oxide nano-particle is zero, has superparamagnetism.
Description of drawings
Fig. 1 is the TEM figure of Fe nanometer particles
Fig. 2 is the HRTEM figure of Fe nanometer particles
Fig. 3 is the XRD figure of Fe nanometer particles
Fig. 4 is the hysteresis curve of Fe nanometer particles
Fig. 5 is the TEM figure of Fe nanometer particles
Fig. 6 is the HRTEM figure of Fe nanometer particles
Fig. 7 is the XRD figure of Fe nanometer particles
Fig. 8 is the TEM figure of ferriferrous oxide nano-particle
Fig. 9 is the HRTEM of ferriferrous oxide nano-particle
Figure 10 is the XRD figure of ferriferrous oxide nano-particle
Figure 11 is the hysteresis curve of ferriferrous oxide nano-particle
The invention effect
The present invention compared with prior art has following outstanding technical characterstic:
The gained nano particle turns out to be pure iron through X-ray diffraction analysis (XRD); Transmission electron microscope analysis, average grain diameter are 11.5 nanometers, particle diameter distribution standard deviation σ=3.5%; The superconductive quantum interference magnetometric analysis shows that specific saturation magnetization is 121emu/g, and the magnetic resistance of Fe nanometer particles is zero in the time of 25 ℃, has superparamagnetism.
Claims (1)
1. the preparation of a monodisperse amorphous state nickel nano particle and separation method, this method is to be raw material with the ferric acetyl acetonade, atoleine is a reaction medium, tri octyl phosphine and oleyl amine are the nano particle stabilizing agent, polyalcohol is that the reaction of nano particle pattern dressing agent forms, it is characterized in that in tank reactor, above-mentioned substance being mixed by a certain percentage, be 40 milliliters of atoleines, ferric acetyl acetonade 2 mMs, tri octyl phosphine and oleyl amine respectively are 6 mMs, and polyalcohol 2 mMs feed hydrogen then, be warming up to 300 ℃ then, reacted 2-5 hour; Treat that kettle is cooled to room temperature, take out reactant liquor and put into beaker, add 50 milliliters of 5: 1 ethanol and benzinum, leave standstill after fully stirring; Beaker is placed on forever on the strong magnet, and can observe the liquid layering this moment; Remove supernatant liquor, repeat above-mentioned steps, be enriched in beaker bottom, powder is placed vacuum drying chamber until the black powder, under 100 ℃ and 1 millimetres of mercury condition dry 1 hour, can obtain nano particle after the cooling, place storage under the nitrogen protection then;
Wherein, polyalcohol is 1,2-16 glycol.
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