CN102504820B - Preparation method of up-conversion fluorescence/paramagnetic difunctional nanocrystal - Google Patents
Preparation method of up-conversion fluorescence/paramagnetic difunctional nanocrystal Download PDFInfo
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Abstract
The invention discloses a preparation method of up-conversion fluorescence/paramagnetic difunctional nanocrystal, relating to a luminescent nanometer material. A quick and environment-friendly preparation method of up-conversion fluorescence/paramagnetic difunctional nanocrystal is provided, which comprises the following steps: dissolving rare-earth oxide in a determined molar ratio into hydrochloric acid or nitric acid solution to obtain chloride or nitrate solution mixed with various rare-earth elements; mixing sodium hydroxide, oleic acid, ethanol and water; fully stirring the mixture to obtain a homogeneous solution; adding rare-earth chloride or nitrate solution and sodium fluoride water solution, and fully mixing to obtain reaction precursor; and performing microwave synthesis of the reaction precursor solution, and after the reaction stops, centrifugating, washing and drying the product to obtain up-conversion fluorescence/paramagnetic difunctional nanocrystal. The preparation method well combines the ethanol/water solvent system and the microwave heating, is green and environment-friendly, has simple process, is easy to obtain cheap raw materials and has high efficiency; the product has regular shape, uniform size and good dispersity and has up-conversion fluorescence and paramagnetic properties.
Description
Technical field
The present invention relates to a kind of Illuminant nanometer material, particularly relate to the difunctional preparation of nano crystal of a kind of up-conversion fluorescence/paramagnetism.
Background technology
The up-conversion luminescence process that multi-photon participates in can convert long-wavelength excitation light to short wavelength and launch light.Because its unique luminescent properties, up-conversion luminescent material has important application in many-sides such as solid statelaser, fiber amplifier, anti-counterfeiting technology, stereo display, solar cells.In recent years, in the fluoroscopic examination of cell and tissue and the fields such as diagnosis of mark, biomolecules identification and disease, rear-earth-doped up-conversion luminescence nano material has been subjected to extensive concern as biological fluorescent labeling.Rear-earth-doped up-conversion luminescence nano material can realize near infrared, visible even ultraviolet light emission under the exciting of near infrared light.Advantages such as this type of material also has biological tissue's " optical transparence ", good light stability, chemical stability is good, bio-toxicity is low, therefore the up-conversion luminescence nano material is expected to become the desirable biological fluorescent labeling (Chem.Soc.Rev. with huge applications prospect, 2009,38,976-989).
With hexagonal crystal phase NaYF
4For the up-conversion luminescent material of matrix is considered to the highest up-conversion luminescent material of luminous efficiency.And use NaGdF
4Replace NaYF
4As the matrix of up-conversion fluorescence nano material, not only can obtain almost and NaYF
4Suitable luminous efficiency during for matrix satisfies the demand of biological fluorescent labelling and detection, and utilizes matrix positively charged ion Gd
3+Good paramagnetic performance, this nanocrystalline can simultaneously (Biomaterials 2010,31,3287-3295) as good magnetic resonance imaging contrast.In addition, with ratio of ionic radii Y
3+Big slightly Gd
3+Replace Y
3+Matrix positively charged ion as conversion nano crystal on this type of will help the mutually nanocrystalline generation of hexagonal crystal, and can clearly shorten the reaction required time, reduces temperature of reaction and improve up-conversion luminescence efficient that (Nature 2010,463,1061-1065).
At present, there have been many methods can be used for preparing uniform particle diameter, NaY (Gd) F that pattern is controlled
4: Ln
3+(Ln:Yb, Er/Tm/Ho) up-conversion fluorescence nanoparticle comprise hydrothermal method, complex-precipitation method, high temperature organic solvent hydrothermal method, sol-gel method etc.Not only there are oversize, shortcomings such as efficient is low, severe reaction conditions, product regularity and bad dispersibility of reaction times to some extent in these preparation methods, and often have been accompanied by toxic byproduct and produce.Because its environmental protection, quick and high energy utilization efficiency, carry out microwave radiation heating is widely used for the organic synthesis field rapidly, and (Nanoscale 2010,2,1358-1374) to be applied to the preparation process of inorganic nano material more and more.Combine the reaction system of carry out microwave radiation heating and cheapness, environmental protection and strong microwave absorbing efficient the synthetic of researchdevelopment new function nano material to have huge research and production exploitation to be worth.But, up to the present, be medium with water/ethanol equal solvent cheap, cleaning, (count in the min) the synthetic rare earth doped conversion nano crystalline substance of going up fast with carry out microwave radiation heating, particularly with NaGdF
4For document and the patent of the dispersed nano crystalline substance that has up-conversion fluorescence and magnetic concurrently of matrix yet there are no open report.
Summary of the invention
The object of the invention be to provide a kind of fast, the difunctional preparation of nano crystal of up-conversion fluorescence/paramagnetism of environmental protection.
The present invention includes following steps:
1) takes by weighing rare earth oxide Gd according to definite mol ratio
2O
3, Yb
2O
3, XO
3Powder joins in the acid solution, and the acid solution of adding is 1～2 times of stoichiometric ratio, and is airtight, places water-bath heating and magnetic agitation to make it to dissolve fully, again solution is heated to evaporate to dryness, and the back in volumetric flask, obtains LnCl with the pure water constant volume
3Mixed solution A, sealing is preserved standby, described XO
3Be ErO
3, TmO
3Or HoO
3Wherein the rare earth element mol ratio is: Gd: ytterbium (Yb): erbium (Er)/thulium (Tm)/holmium (Ho)=(70～90): (10～30): (0.1～5); Described Ln=Gd, Yb/Er, Gd, Yb/Tm or Gd, Yb/Ho; Described acid solution is hydrochloric acid soln or salpeter solution; Described mixed solution A is LnCl
3Mixed solution A or LnNO
3Mixed solution A;
2) measure sodium hydroxide solution and join in the oleic acid, stir and obtain white sodium oleate solid, in whipping process, dissolve the sodium oleate solid with dehydrated alcohol, obtain the homogeneous phase transparent solution B;
3) in solution B, add mixed solution A and Fluorinse, reactant is fully mixed, obtain the translucent solution C of homogeneous phase;
4) get the translucent solution C of homogeneous phase and join in the crystal reaction tube of microwave synthesizer, sealing, the microwave synthesizer of packing into carries out the microwave building-up process;
5) after question response stops, taking out reaction vessel, add the dehydrated alcohol supersound washing, the centrifugation product, repeated washing, centrifugal process obtain NaGdF after the drying
4: the last conversion of Ln/paramagnetism manocrystalline powders, described Ln=Yb, Er/Tm/Ho.
In step 1), the massfraction of described acid solution can be 10%～20%; The temperature of described water-bath can be 75～85 ℃.
In step 2) in, described sodium hydroxide solution: oleic acid: the volume ratio of dehydrated alcohol can be (2～5): (10～20): (5～15), the concentration of described sodium hydroxide solution can be 1～4mol/L.
In step 3), described mixed solution A: the volume ratio of Fluorinse can be (2～5): (4～10), the concentration of described Fluorinse can be 0.5～2mol/L.
In step 4), the synthetic condition of described microwave can be 120～180 ℃ of temperature of reaction, reaction times 1～30min.
In step 5), described centrifugal speed can adopt 4000～10000rpm; Described repeated washing, centrifugal process can carry out 3 times; The condition of described drying can be 40～80 ℃ of following vacuum-drying 5～24h, or lyophilize.
The typical product that the present invention obtains be length less than 150nm, diameter is less than the dispersed nano rod of 20nm, by changing the amount of reactant middle-weight rare earths muriate (or rare earth nitrate) and Sodium Fluoride simultaneously, it is nanocrystalline to obtain diameter 10～30nm particulate state.This crystalline material has conversion and paramagnetism dual-use function near infrared-near infrared/visible/Ultraluminescence concurrently.
The present invention uses single mode focused microwave synthesis system, muriate or nitrate with rare-earth element gadolinium, ytterbium, erbium, thulium, holmium etc., Sodium Fluoride, Neutral ammonium fluoride or ammonium bifluoride etc. are the principal reaction thing, be anion surfactant with the sodium oleate, be the solvent main microwave absorbing medium of holding concurrently with the ethanol/water, what keep under 120～180 ℃ of temperature of reaction that 1～30min can obtain regular pattern has up-conversion fluorescence/paramagnetic hexagonal crystal phase NaGdF concurrently
4: Yb, Er/Tm/Ho dispersed nano crystalline substance.Reaction system with second alcohol and water with strong polarity as main reaction solvent, it is not only a kind of cheap and easy to get, environmentally friendly reaction system, and, because they all are good microwave absorbing media, reaction only needs very low microwave transmitted power, and (15～40W) can reach and keep the required temperature of reaction rapidly.The more important thing is that microwave radiation replaces traditional heating to make the required reaction times shorten to several min by a few hours even tens of hours, has greatly improved efficient, and the enormous industrialization DEVELOPMENT PROSPECT is arranged.
Compared with prior art, the present invention has following remarkable advantage:
1) use cheapness, the second alcohol and water of cleaning combines as reaction solvent and carry out microwave radiation heating, has developed a kind of environmental protection, the fast and convenient upward difunctional preparation of nanomaterials of conversion/paramagnetism.
2) because the second alcohol and water all is good microwave absorbing medium, reaction only needs very low microwave transmitted power can reach and keep the required temperature of reaction rapidly, is the high preparation method of nano material of a kind of capacity usage ratio.Carry out microwave radiation heating makes similar reactant system finish reaction under traditional heating mode and required a few hours even tens of hours shortens to several min, shortened the reaction times very significantly, and make the temperature of reaction more than 160 ℃ that needs under the traditional heating mode be reduced to 120 ℃, reduced and finished the required temperature of reaction.These have all greatly improved working efficiency, and the enormous industrialization DEVELOPMENT PROSPECT is arranged.
3) NaGdF that obtains of present method
4: Yb, Er/Tm/Ho not only has from Yb, the polychrome up-conversion fluorescence of Er/Tm/Ho, and have from matrix positively charged ion Gd
3+Paramagnetism, thereby merge up-conversion fluorescence, paramagnetism is one, is a kind of multi-functional nanometer material that significant application value is arranged in biomedicine.
4) present method obtains goes up that conversion/paramagnetism is nanocrystalline to show extraordinary monodispersity, can control products therefrom and is long 20～100nm by changing reactant concn, and the regular bar-shaped or diameter 10-20nm particulate state pattern of diameter 5～20nm is nanocrystalline.
Description of drawings
Fig. 1 is the real-time surveillance map of rapid microwave building-up process temperature-power among the embodiment 2.In Fig. 1, X-coordinate is Time (mm:ss), vertical sit for temperature T emp (℃).
Fig. 2 is embodiment 1～5 prepared NaGdF
4: Yb, the X-ray diffractogram that Er is nanocrystalline.In Fig. 2, in Fig. 2, X-coordinate be diffraction angle 2 θ/°, ordinate zou is intensity/a.u.; Curve (a) is embodiment 1, and curve (b) is embodiment 2, and curve (c) is embodiment 3, and curve (d) is embodiment 4, and curve (e) is embodiment 5.
Fig. 3 is embodiment 1 obtained NaGdF
4: Yb, the transmission electron microscope photo that Er is nanocrystalline.In Fig. 3, scale is 100nm.
Fig. 4 is embodiment 2 obtained NaGdF
4: Yb, the transmission electron microscope photo that Er is nanocrystalline.In Fig. 4, scale is 100nm.
Fig. 5 is embodiment 3 obtained NaGdF
4: Yb, the transmission electron microscope photo that Tm is nanocrystalline.In Fig. 5, scale is 20nm.
Fig. 6 is embodiment 4 obtained NaGdF
4: Yb, the transmission electron microscope photo that Tm is nanocrystalline.In Fig. 6, scale is 100nm.
Fig. 7 is embodiment 5 obtained NaGdF
4: Yb, the transmission electron microscope photo that Ho is nanocrystalline.In Fig. 7, scale is 100nm.
Fig. 8 is that embodiment 1,3 and 5 prepared up-conversion fluorescence spectrograms and 980nm near-infrared laser excite down corresponding nanocrystalline colloidal solution fluorescence photo.In Fig. 8, (a) be embodiment 1 prepared NaGdF
4: Yb, Er (b) up-conversion fluorescence spectrogram and 980nm near-infrared laser excite down corresponding nanocrystalline colloidal solution fluorescence photo; (b) be embodiment 3 prepared NaGdF
4: Yb, Tm (c) up-conversion fluorescence spectrogram and 980nm near-infrared laser excite down corresponding nanocrystalline colloidal solution fluorescence photo; (c) be embodiment 5 prepared NaGdF
4: Yb, the up-conversion fluorescence spectrogram of Ho (a) and 980nm near-infrared laser excite down corresponding nanocrystalline colloidal solution fluorescence photo; X-coordinate is wavelength (nm), and ordinate zou is intensity (a.u.).
Fig. 9 obtains NaGdF for detecting among the embodiment 1 with superconductive quantum interference magnetometer (MPMS-XL-7)
4: Yb, the nanocrystalline low temperature that obtains of Er (2K) magnetic hysteresis loop figure, its saturation magnetization is 98.78emu/g (40kOe).In Fig. 9, X-coordinate is specific magnetising moment Applied magnetic field (Oe), and ordinate zou is magneticstrength Magnetization (emu/g).
Figure 10 obtains NaGdF for detecting among the embodiment 1 with superconductive quantum interference magnetometer (MPMS-XL-7)
4: Yb, the nanocrystalline M-T figure that obtains of Er.The NaGdF that the susceptible of proof of being combined with Fig. 9 obtains
4: Yb, Er is nanocrystalline to be paramagnetic substance.In Figure 10, X-coordinate is temperature (K), and ordinate zou is magneticstrength Magnetization (emu/g).
Embodiment
Following examples will the invention will be further described by reference to the accompanying drawings.
Embodiment 1
(a) be 80%Gd according to mol ratio, 18%Yb, 2%Er accurately take by weighing rare earth oxide 725mg (2mmol) Gd
2O
3, 177.35mg (0.45mmol) Yb
2O
3, 19.13mg (0.05mmol) Er
2O
3In the 50ml flask, adding 5ml pure water and 5ml concentration are 37.5% concentrated hydrochloric acid, and is airtight, place 80～85 ℃ of water-bath heating and magnetic agitation to make it to dissolve fully, again solution slowly is heated to evaporate to dryness, back constant volume obtains the LnCl of 0.2mol/L in the 25ml volumetric flask
3(Ln=80%Gd, 18%Yb, 2%Er) solution A, sealing is preserved standby.
(b) 0.8g NaOH, 4ml H
2O, 13ml oleic acid, 7ml ethanol mixes in the process that stirs, and obtains the homogeneous phase transparent solution B.
(c) in the whipping process, add 2ml 02mol/L solution A successively in the solution B and 3ml 1mol/LNaF solution obtains the translucent solution C of homogeneous phase.
(d) get from C in the 10mL quartz reactor that the 7ml reactant solution joins CEM single mode focused microwave synthesizer, with the sealing of blowout disk plug, put into the microwave synthesizer, the microwave synthetic parameters is set: power 30W keeps 160 ℃ of temperature, hold-time 5min.Start-up routine carries out microwave and synthesizes.
(e) after question response stops, taking out reactor, add the supersound washing of 10ml dehydrated alcohol, collect product, the NaGdF that obtains behind the centrifugation product, repeated washing/centrifugal process 4 times
4: Yb, Er is nanocrystalline stably to be dispersed in non-polar solvent with the transparent colloidal solution form, in hexanaphthene, excites down at the 980nm near-infrared laser, and the up-conversion fluorescence spectrum of its colloidal solution and fluorescence photo are seen Fig. 8 (b).Or after the lyophilize, obtain conversion/paramagnetism manocrystalline powders.Analyze collection of illustrative plates and transmission electron microscope (TEM) pattern photo shown in Figure 3 referring to the powder x-ray diffraction (XRD) shown in Fig. 2 (a).
Fig. 9 provides with obtaining NaGdF among superconductive quantum interference magnetometer (MPMS-XL-7) the detection embodiment 1
4: Yb, the nanocrystalline low temperature that obtains of Er (2K) magnetic hysteresis loop figure, its saturation magnetization is 98.78emu/g (40kOe).
Figure 10 provides with obtaining NaGdF among superconductive quantum interference magnetometer (MPMS-XL-7) the detection embodiment 1
4: Yb, the nanocrystalline M-T figure that obtains of Er.The NaGdF that the susceptible of proof of being combined with Fig. 9 obtains
4: Yb, Er is nanocrystalline to be paramagnetic substance.
Embodiment 2
(a) be 78%Gd according to mol ratio, 20%Yb, 2%Er accurately take by weighing rare earth oxide 1.41g (3.9mmol) Gd
2O
3, 394.08mg (1mmol) Yb
2O
3, 38.25mg (0.1mmol) Er
2O
3In flask, add the concentrated hydrochloric acid of 10ml pure water and 10ml 37.5% concentration, airtight, place 80～85 ℃ of water-bath heating and magnetic agitation to make it to dissolve fully, again solution slowly is heated to evaporate to dryness, back constant volume obtains the LnCl of 0.4mol/L in the 25ml volumetric flask
3(Ln=78%Gd, 20%Yb, 2%Er) solution A, sealing is preserved standby.
(b) 0.8g NaOH, 4ml H
2O, 13ml oleic acid, 7ml ethanol mixes in the process that stirs, and obtains the homogeneous phase transparent solution B.
(c) in the whipping process, add 1ml 0.4mol/L solution A successively in the solution B and 3ml 1mol/L NaF solution obtains the translucent solution C of homogeneous phase
(d) get from C in the 10mL quartz reactor that the 5ml reactant solution joins CEM single mode focused microwave synthesizer, with the sealing of blowout disk plug, put into the microwave synthesizer, the microwave synthetic parameters is set: power 30W keeps 180 ℃ of temperature, hold-time 1min.Start-up routine carries out microwave and synthesizes.
(e) after question response stops, taking out reactor, add the supersound washing of 10ml dehydrated alcohol, collect product behind the centrifugation product, repeated washing/centrifugal process 4 times, after the lyophilize, obtain NaGdF
4: Yb, the last conversion of Er/paramagnetism manocrystalline powders.Analyze collection of illustrative plates and transmission electron microscope (TEM) pattern photo shown in Figure 4 referring to the powder x-ray diffraction (XRD) shown in Fig. 2 (b).Fig. 1 provides the real-time surveillance map of rapid microwave building-up process temperature-power among the embodiment 2.
Embodiment 3
(a) be 59.5%Gd according to mol ratio, 40%Yb, 0.5%Tm accurately take by weighing rare earth oxide 1078.44mg (2.975mmol) Gd
2O
3, 788.16mg (2.0mmol) Yb
2O
3, 9.65mg (0.025mmol) Tm
2O
3In flask, add the concentrated nitric acid of 5ml pure water and 3ml 68% concentration, airtight, place 80～85 ℃ of water-bath heating and magnetic agitation to make it to dissolve fully, again solution slowly is heated to evaporate to dryness, back constant volume obtains the LnNO of 0.4mol/L in the 25ml volumetric flask
3(Ln=59.5%Gd, 40%Yb, 0.5%Tm) solution A, sealing is preserved standby.
(b) 0.8g NaOH, 4ml H
2O, 13ml oleic acid, 7ml ethanol mixes in the process that stirs, and obtains the homogeneous phase transparent solution B.
(c) in the whipping process, add 2ml 0.4mol/L solution A successively in the solution B and 6ml 1mol/L NaF solution obtains the translucent solution C of homogeneous phase.
(d) get from C in the 10mL quartz reactor that the 5ml reactant solution joins CEM single mode focused microwave synthesizer, with the sealing of blowout disk plug, put into the microwave synthesizer, the microwave synthetic parameters is set: power 30W keeps 160 ℃ of temperature, hold-time 5min.Start-up routine carries out microwave and synthesizes.
(e) after question response stops, taking out reactor, add the 10ml absolute ethanol washing, collect product, the NaGdF that obtains behind the centrifugation product, repeated washing/centrifugal process 4 times
4: Yb, Tm is nanocrystalline stably to be dispersed in non-polar solvent with the transparent colloidal solution form, in hexanaphthene, excites down at the 980nm near-infrared laser, and the up-conversion fluorescence spectrum of its colloidal solution and fluorescence photo are shown in Fig. 8 (c).Or after the lyophilize, obtain NaGdF
4: Yb, the last conversion of Tm/paramagnetism manocrystalline powders.Analyze collection of illustrative plates and transmission electron microscope (TEM) pattern photo shown in Figure 5 referring to the powder x-ray diffraction (XRD) shown in Fig. 2 (c).
Embodiment 4
(a) be 59.5%Gd according to mol ratio, 40%Yb, 0.5%Tm accurately take by weighing rare earth oxide 1078.44mg (2.975mmol) Gd
2O
3, 788.16mg (2.0mmol) Yb
2O
3, 9.65mg (0.025mmol) Tm
2O
3In flask, adding 10ml pure water and 5ml concentration are 68% concentrated nitric acid, and is airtight, places 80～85 ℃ of water-baths heating and magnetic agitation to make it to dissolve fully, again solution slowly is heated to evaporate to dryness, and back constant volume obtains the LnNO of 0.4mol/L in the 25ml volumetric flask
3(Ln=59.5%Gd, 40%Yb, 0.5%Tm) solution, sealing is preserved standby.
(b) 0.8g NaOH, 4ml H
2O, 13ml oleic acid, 7ml ethanol mixes in the process that stirs, and obtains the homogeneous phase transparent solution B.
(c) in the whipping process, add 1ml 0.4mol/L solution A successively in the solution B and 3ml 1mol/L NaF solution obtains the translucent solution C of homogeneous phase.
(d) get from C in the 10mL quartz reactor that the 5ml reactant solution joins CEM single mode focused microwave synthesizer, with the sealing of blowout disk plug, put into the microwave synthesizer, the microwave synthetic parameters is set: power 30W keeps 120 ℃ of temperature, hold-time 30min.Start-up routine carries out microwave and synthesizes.
(e) after question response stops, taking out reactor, add the supersound washing of 10ml dehydrated alcohol, collect product behind the centrifugation product, repeated washing/centrifugal process 4 times, after the lyophilize, obtain NaGdF
4: Yb, the last conversion of Tm/paramagnetism manocrystalline powders.Analyze collection of illustrative plates and transmission electron microscope (TEM) pattern photo shown in Figure 6 referring to the powder x-ray diffraction (XRD) shown in Fig. 2 (d).
Embodiment 5
(a) be 75%Gd according to mol ratio, 20%Yb, 5%Ho accurately take by weighing rare earth oxide 1.36g (3.75mmol) Gd
2O
3, 394.08mg (1.0mmol) Yb
2O
3, 94.47mg (0.25mmol) Ho
2O
3In flask, adding 10ml pure water and 8ml concentration are 68% concentrated nitric acid, and is airtight, places 80～85 ℃ of water-baths heating and magnetic agitation to make it to dissolve fully, again solution slowly is heated to evaporate to dryness, and back constant volume obtains the LnNO of 0.4mol/L in the 25ml volumetric flask
3(Ln=75%Gd, 20%Yb, 5%Tm) solution A, sealing is preserved standby.
(b) 0.8g NaOH, 4ml H
2O, 13ml oleic acid, 7ml ethanol mixes in the process that stirs, and obtains the homogeneous phase transparent solution B.
(c) in the whipping process, add 1ml 0.4mol/L solution A successively in the solution B and 3ml 1mol/L NaF solution obtains the translucent solution C of homogeneous phase.
(d) get from C in the 10mL quartz reactor that the 5ml reactant solution joins CEM single mode focused microwave synthesizer, with the sealing of blowout disk plug, put into the microwave synthesizer, the microwave synthetic parameters is set: power 30W keeps 140 ℃ of temperature, hold-time 10min.Start-up routine carries out microwave and synthesizes.
(e) after question response stops, taking out reactor, add the 5ml absolute ethanol washing, collect product, the NaGdF that obtains behind the centrifugation product, repeated washing/centrifugal process 4 times
4: Yb, Ho is nanocrystalline stably to be dispersed in the hexanaphthene with the transparent colloidal solution form, excites down at the 980nm near-infrared laser, and the up-conversion fluorescence spectrum of its colloidal solution and fluorescence photo are shown in Fig. 8 (a).Or after the lyophilize, obtain NaGdF
4: Yb, the last conversion of Ho/paramagnetism manocrystalline powders.Analyze collection of illustrative plates and transmission electron microscope (TEM) pattern photo shown in Figure 7 referring to the powder x-ray diffraction (XRD) shown in Fig. 2 (e).
Claims (8)
1. difunctional preparation of nano crystal of up-conversion fluorescence/paramagnetism is characterized in that may further comprise the steps:
1) takes by weighing rare earth oxide Gd according to definite mol ratio
2O
3, Yb
2O
3, XO
3Powder joins in the acid solution, and the acid solution of adding is 1～2 times of stoichiometric ratio, and is airtight, place water-bath heating and magnetic agitation to make it to dissolve fully, again solution is heated to evaporate to dryness, the back uses the pure water constant volume in volumetric flask, obtain mixed solution A, sealing is preserved standby, described XO
3Be ErO
3, TmO
3Or HoO
3Wherein the rare earth element mol ratio is: Gd: Yb: Er/Tm/Ho=(70～90): (10～30): (0.1～5); Described acid solution is hydrochloric acid soln or salpeter solution;
2) measure sodium hydroxide solution and join in the oleic acid, stir and obtain white sodium oleate solid, in whipping process, dissolve the sodium oleate solid with dehydrated alcohol, obtain the homogeneous phase transparent solution B;
3) in solution B, add mixed solution A and Fluorinse, reactant is fully mixed, obtain the translucent solution C of homogeneous phase; Described mixed solution A: the volume ratio of Fluorinse is (2～5): (4～10), the concentration of described Fluorinse are 0.5～2mol/L;
4) get the translucent solution C of homogeneous phase and join in the crystal reaction tube of microwave synthesizer, sealing, the microwave synthesizer of packing into carries out the microwave building-up process;
5) after question response stops, taking out reaction vessel, add the dehydrated alcohol supersound washing, the centrifugation product, repeated washing, centrifugal process obtain NaGdF after the drying
4: the last conversion of Ln/paramagnetism manocrystalline powders, described Ln=Yb, Er/Tm/Ho.
2. the difunctional preparation of nano crystal of a kind of up-conversion fluorescence/paramagnetism as claimed in claim 1 is characterized in that in step 1), and the massfraction of described acid solution is 10%～20%.
3. the difunctional preparation of nano crystal of a kind of up-conversion fluorescence/paramagnetism as claimed in claim 1 is characterized in that in step 1), and the temperature of described water-bath is 75～85 ℃.
4. the difunctional preparation of nano crystal of a kind of up-conversion fluorescence/paramagnetism as claimed in claim 1, it is characterized in that in step 2) in, described sodium hydroxide solution: oleic acid: the volume ratio of dehydrated alcohol can (2～5): (10～20): (5～15), the concentration of described sodium hydroxide solution are 1～4mol/L.
5. the difunctional preparation of nano crystal of a kind of up-conversion fluorescence/paramagnetism as claimed in claim 1 is characterized in that in step 4), and the synthetic condition of described microwave is 120～180 ℃ of temperature of reaction, reaction times 1～30min.
6. the difunctional preparation of nano crystal of a kind of up-conversion fluorescence/paramagnetism as claimed in claim 1 is characterized in that in step 5), and described centrifugal speed adopts 4000～10000rpm.
7. the difunctional preparation of nano crystal of a kind of up-conversion fluorescence/paramagnetism as claimed in claim 1 is characterized in that in step 5), and described repeated washing, centrifugal process carry out 3 times.
8. the difunctional preparation of nano crystal of a kind of up-conversion fluorescence/paramagnetism as claimed in claim 1 is characterized in that in step 5), and the condition of described drying is 40～80 ℃ of following vacuum-drying 5～24h, or lyophilize.
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| CN105295892A (en) * | 2015-11-24 | 2016-02-03 | 西南民族大学 | Preparation method of core-shell structured magnetic up-conversion luminescence bifunctional nano-particles |
| CN105670629A (en) * | 2016-02-19 | 2016-06-15 | 青岛大学 | Low temperature synthesis method for infrared excitation up-conversion nano material NaGdF4:Yb3+/Tm3+ |
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