CN101289217B - Hydro-thermal synthesis process of microemulsion of amphipathic rare-earth nano material - Google Patents
Hydro-thermal synthesis process of microemulsion of amphipathic rare-earth nano material Download PDFInfo
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Abstract
The invention belongs to the technical field of nano materials, in particular to a microemulsion hydrothermal synthesizing method for an amphipathy rare earth nano material. In the method, the water solution of rare earth compound and the water solution of double-function ligand are taken as the water phase, a non-polar organic solvent is taken as the oil phase and a surfactant is added for preparing an inverting microemulsion system. The water solution of fluoride or phosphate or vanadate is taken as the water phase, the non-polar organic solvent is taken as the oil phase and the surfactant is added for preparing another inverting microemulsion system. The two inverting microemulsion systems are respectively stirred to obtain colorless solution which are mixed and evenly stirred; then the mixed solution is transferred to a water-heating kettle for water-heating. After cooling, appropriate amount of acetone is added for demulsification and high speed centrifugation; then n-heptane and ethanol are used in sequence for washing and sedimentation, thus obtaining the rare earth nano material after drying in vacuum. The surface of the rare earth nano material has the double-function ligand and the surfactant, thus leading the double-function ligand and the surfactant to have hydrophilic property and hydrophobic property.
Description
Background technology
The invention belongs to technical field of nano material, be specifically related to a kind of hydro-thermal synthesis process of microemulsion of amphipathic rare-earth nano material.
Background technology
The application of rare earth nano material relates to every field, has a wide range of applications in machinery, electronics, optics, magnetics, chemistry and biology field.Particularly rare earth luminous nano material has advantages such as emission is narrow, life-span length, bleach-resistant, is having major application to be worth aspect biomarker and the imaging.The biologic applications prerequisite of rare earth nano material is: (1) surface have active group (as-COOH ,-NH
2Perhaps-SH), be convenient to they and biomolecular reaction; (2) have amphipathicly, wherein wetting ability helps rare earth nano material and is scattered in water, and hydrophobicity (lipophilicity) helps rare earth nano material and enters cytolemma; (3) its size is less and pattern is controlled; (4) luminous efficiency is higher.
Usually the rare earth nano material periphery that utilizes the tensio-active agent aid preparation to become is an alkyl chain, so they generally are hydrophobic, also is difficult to further functionalization.For example utilize typical hydrothermal method (Li YD, Nature 2005,437,121; InorganicChemistry 2006,45, and 6661) or pyrolysis method (Capobianco J A et al.Journal of the American ChemicalSociety, 2006,128,7444; Yan CH, Journal of the American Chemical Society 2005,127,3260) or reverse microemulsion method (Lemyre JL et a1.Chemistry of Materials, 2005,17,3040.) etc. there is long alkyl chain on the rare earth nano material surface of preparation, thereby all be hydrophobic, can only be dissolved in non-polar organic solvent.Current improvement strategy commonly used is at the surface of rare earth nano material parcel one deck SiO
2Perhaps macromolecular material, this parcel can improve water-soluble, also can provide active function groups, but complex process, the cost height of the synthetic required rare earth nano material of this two-step approach.
Summary of the invention
The present invention proposes general preparation method a kind of functionalization, amphipathic rare-earth nano material, this method is assisted tensio-active agent step preparation amphipathic rare-earth nano material in the reverse microemulsion system by double function ligand.
The hydro-thermal synthesis process of microemulsion of the amphipathic rare-earth nano material that the present invention proposes, concrete steps are as follows:
(1) preparation reverse microemulsion liquid system
With the 0.001-0.5 mol rare earth compound aqueous solution and 0.001-0.5 mol double function ligand aqueous solution, wherein two kinds of aqueous solution volumes add up to the 0.1-4 milliliter, mol ratio between rare earth compound and the double function ligand is 1: 1～1: 10, be water with this mixed aqueous solution then, with 10-100 milliliter non-polar organic solvent is oil phase, adds first kind of reverse microemulsion liquid system of tensio-active agent preparation; Being water with the fluorochemical of 0.1-8 milliliter 0.001-1 mol or phosphoric acid salt or the vanadate aqueous solution again, is oil phase with 10-100 milliliter non-polar organic solvent, adds second kind of reverse microemulsion liquid system of tensio-active agent preparation; The mol ratio of water and tensio-active agent is 1-80 in two kinds of reverse microemulsion liquid system; Two kinds of reverse microemulsion liquid system were stirred respectively 0.1-5 hour, obtain limpid colourless liquid;
(2) hydro-thermal reaction prepares rare earth nano material
Two kinds of reverse micro emulsions that step (1) is obtained mix, and stir after 5-60 minute, and mixing solutions is transferred to water heating kettle, encapsulate, 100-250 ℃ of hydrothermal treatment consists 0.5～30 hour.Behind the naturally cooling, add the acetone breakdown of emulsion, high speed centrifugation 5-60 minute again.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation again, remove adsorbed organic matter after, the vacuum-drying precipitation promptly obtains amphipathic rare earth nano material.
The rare earth nano material surface of the present invention's preparation has double function ligand and tensio-active agent simultaneously, causes its possess hydrophilic property and hydrophobicity (lipophilicity) simultaneously.
Rare earth compound among the present invention is the muriate or the nitrate of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) or yttrium (Y), or wherein several mixtures.
Double function ligand among the present invention is X-(CH
2)
n-Y, wherein radicals X be-COOH ,-SH ,-NH
2Perhaps-OH; Group Y is-COOH ,-SH ,-NH
2Perhaps-OH; N is the natural number of 1-30.
The non-polar organic solvent as oil phase among the present invention is normal hexane, normal heptane, octane-iso, toluene or benzene.
Tensio-active agent among the present invention can use soap (RCOO
-M
+), sulfonate (R-SO
3 -M
+), sulfuric acid (R-OSO
3Na) or alkyl phosphate salt.
The preferred succsinic acid two of tensio-active agent among the present invention (2-ethylhexyl) ester sodium sulfonate (being called for short AOT), Sodium dodecylbenzene sulfonate (being called for short LAS), sodium lauryl sulphate salt (being called for short SDS).
Fluorochemical among the present invention or phosphoric acid salt or vanadate are generally their sodium salt, sylvite or ammonium salt.
Preparation method's cost of the present invention is low, easy, general, and the rare earth nano material of preparation has good amphipathic, can be applicable to biological field, is having major application to be worth aspect biomarker and the bio-imaging.
Description of drawings
Fig. 1 is amphipathic NaYF
4: 20mol%Yb, the transmission electron microscope photo of 2mol%Er nano particle.
Fig. 2 is amphipathic NaYF
4: 20mol%Yb, the infrared spectra of 2mol%Er nano particle.
Fig. 3 is amphipathic NaYF
4: 20mol%Yb, the fluorescence spectrum of the aqueous solution of 2mol%Er nano particle under the 980nm laser apparatus excites.
Fig. 4 is amphipathic LaF
3: 20mol%Yb, the fluorescence spectrum of the aqueous solution of 2mol%Tm nano particle under the 980nm laser apparatus excites.
Embodiment
The invention will be further described by the following examples, but the present invention is not constituted any limitation.
The amphipathic NaYF of embodiment 1 preparation
4: 20mol%Yb, 2mol%Er nano particle
With the 40mL normal heptane is oil phase, is tensio-active agent with AOT (0.075M), with the 6-aminocaprolc acid aqueous solution (0.4mL, 0.375mol/L serve as double function ligand) and aqueous solution of rare earth chloride (0.2ml, 0.5mol/L LnCl
3, Ln:78mol%Y+20mol%Yb+2mol%Er) be water, prepared first kind of reverse microemulsion system.With the 40mL normal heptane is oil phase, is tensio-active agent with AOT (0.075M), and (0.6ml 1mol/L) is water, has prepared second kind of reverse microemulsion system with the NaF aqueous solution.Two kinds of reverse microemulsion systems stir about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, and stir about 20min.Mixture is transferred to the 100mL water heating kettle, and encapsulation is at 180 ℃ of hydrothermal treatment consists 6h.Behind the naturally cooling, add the proper amount of acetone breakdown of emulsion, and more at a high speed (12,000rpm) centrifugal 20min.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed AOT and other impurity of absorption several times again.The vacuum-drying precipitation obtains amphipathic NaYF
4: Yb, Er nano particle.Their pattern and particle diameter adopt determination of transmission electron microscopy, and typical results is seen shown in Figure 1, typical NaYF
4: Yb, the Er sample is the silk cocoon shape, and diameter is about 20nm, and length is 20～40nm.The infrared spectra of this material is seen Fig. 2, and wherein many absorption bands have shown the existence of organic ligand.For example, be positioned at 1049 and 1154cm
-1The absorption at place is corresponding to symmetric (v
s) and asymmetric (v
As)-the flexible vibrations of S=O, and should-S=O derives from the sulfonic acid group of AOT part, rather than the sulfonic acid group of AOT molecule freely, and NaYF has been described
4: Yb, there is the AOT part in the Er particle surface.At 1611cm
-1The absorption band at place is corresponding to the flexible vibrations of-COO-.Can infer these chemical groups (O-H or N-H ,-CH
2-,-COO-) may come from AOT and 6-aminocaprolc acid, perhaps come from the intermolecular polymkeric substance of 6-aminocaprolc acid.Quantitative test finds that the amino density on surface is (9.5 ± 0.8) * 10
-5Mol/g.Owing to have 6-aminocaprolc acid and AOT part simultaneously, sample has amphipathic, and has active group (NH
2).Under the exciting of 980nm laser apparatus, this material presents typical green glow (520-570nm) and ruddiness (650-670nm) and goes up switching emission in water, green glow corresponding to from
2H
11/2With
4S
3/2Arrive
4I
15/2Transition; Ruddiness corresponding to from
4F
9/2Arrive
4I
15/2Transition.
The amphipathic LaF of embodiment 2 preparations
3: 20mol%Yb, 2mol%Tm nano particle
With the 40mL normal heptane is oil phase, is tensio-active agent with AOT (0.075M), with the 6-aminocaprolc acid aqueous solution (0.4mL, 0.5mol/L serve as double function ligand) and aqueous solution of rare earth chloride (0.2ml, 0.5mol/L LnNO
3, Ln:78mol%La+20mol%Yb+2mol%Tm) be water, prepared first kind of reverse microemulsion system.With the 40mL normal heptane is oil phase, is tensio-active agent with AOT (0.075M), with NH
4(0.6ml 1mol/L) is water to the F aqueous solution, has prepared second kind of reverse microemulsion system.Two kinds of reverse microemulsion systems stir about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, and stir about 20min.Mixture is transferred to the 100mL water heating kettle, and encapsulation is at 160 ℃ of hydrothermal treatment consists 10h.Behind the naturally cooling, add the proper amount of acetone breakdown of emulsion, and more at a high speed (12,000rpm) centrifugal 20min.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed AOT and other impurity of absorption several times again.The vacuum-drying precipitation obtains amphipathic LaF
3: 20mol%Yb, 2mol%Tm nano particle.Under the exciting of 980nm laser apparatus, the luminescent spectrum that this material presents in water is seen Fig. 4.Have 4 emission bands as can be seen, the emission band of two bluenesss (440～500nm) corresponding to
1D
2→
3F
4With
1G
4→
3H
6Transition; Red emission band a little less than in the of one (635～665nm) corresponding to
1G
4→
3F
4Transition; Extremely strong near infrared emission band (755～840nm) corresponding to
3H
4→
3H
6Transition.
The amphipathic YVO of embodiment 3 preparations
4: 45mol%Ce, 15mol%Tb nano particle
With the 40mL normal heptane is oil phase, is tensio-active agent with LAS (0.05M), with the 12 aqueous solution (0.4mL, 0.375mol/L serve as double function ligand) and aqueous solution of rare earth chloride (0.2ml, 0.5mol/L LnCl
3, Ln:40mol%Y+45mol%Ce+15mol%Tb) be water, prepared first kind of reverse microemulsion system.With the 40mL normal heptane is oil phase, is tensio-active agent with LAS (0.05M), with Na
3VO
4(0.6ml 0.3mol/L) is water to the aqueous solution, has prepared second kind of reverse microemulsion system.Two kinds of reverse microemulsion systems stir about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, and stir about 20min.Mixture is transferred to the 100mL water heating kettle, and encapsulation is at 160 ℃ of hydrothermal treatment consists 6h.Behind the naturally cooling, add the proper amount of acetone breakdown of emulsion, and more at a high speed (12,000rpm) centrifugal 20min.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed the impurity of absorption several times again.The vacuum-drying precipitation obtains amphipathic YVO
4: 45mol%Ce, 15mol%Tb nano particle.Under the exciting of 260nm UV-light, this material presents the feature emission of Tb in water, 489nm corresponding to
5D
4Arrive
7F
6Transition, 542nm corresponding to
5D
4Arrive
7F
5Transition, 582nm corresponding to
5D
4Arrive
7F
4Transition, 619nm corresponding to
5D
4Arrive
7F
3Transition.
The amphipathic LaPO of embodiment 4 preparations
4: the 10mol%Eu nano particle
With the 40mL octane-iso is oil phase, is tensio-active agent with SDS (0.05M), with 3-thiohydracrylic acid (0.1mL serves as double function ligand) and aqueous solution of rare earth chloride (0.6ml, 0.2mol/L, LnCl
3, Ln:90mol%La+10mol%Eu) be water, prepared first kind of reverse microemulsion system.With the 40mL octane-iso is oil phase, is tensio-active agent with SDS (0.05M), with K
3PO
4(0.6ml 0.3mol/L) is water to the aqueous solution, has prepared second kind of reverse microemulsion system.Two kinds of reverse microemulsion systems stir about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, and stir about 20min.Mixture is transferred to the 100mL water heating kettle, and encapsulation is at 200 ℃ of hydrothermal treatment consists 6h.Behind the naturally cooling, add the proper amount of acetone breakdown of emulsion, and more at a high speed (12,000rpm) centrifugal 20min.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed the impurity of absorption several times again.The vacuum-drying precipitation obtains amphipathic LaPO
4: the 10mol%Eu nano particle.Under the exciting of 390nm UV-light, this material presents the feature emission of Eu in water.
The amphipathic LaF of embodiment 5 preparations
3: the 15mol%Tb nano particle
With 40mL toluene is oil phase, is tensio-active agent with AOT (0.1M), with 3-thiohydracrylic acid (0.1mL serves as double function ligand) and aqueous solution of rare earth chloride (0.6ml, 0.2mol/L, LnCl
3, Ln:85mol%La+15mol%Tb) be water, prepared first kind of reverse microemulsion system.With 40mL toluene is oil phase, is tensio-active agent with AOT (0.1M), with NH
4(0.6ml 1mol/L) is water to the F aqueous solution, has prepared second kind of reverse microemulsion system.Two kinds of reverse microemulsion systems stir about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, and stir about 20min.Mixture is transferred to the 100mL water heating kettle, and encapsulation is at 180 ℃ of hydrothermal treatment consists 6h.Behind the naturally cooling, add the proper amount of acetone breakdown of emulsion, and more at a high speed (12,000rpm) centrifugal 20min.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed the impurity of absorption several times again.The vacuum-drying precipitation obtains amphipathic LaF
3: the 15mol%Tb nano particle.Under the exciting of 390nm UV-light, this material presents the feature emission of Tb in water.
The amphipathic GdVO of embodiment 6 preparations
4: 45mol%Ce, 15mol%Tb nano particle
With the 40mL normal heptane is oil phase, is tensio-active agent with LAS (0.05M), with HS-(CH
2)
6-COOH the aqueous solution (0.1mL, 0.5mol/L serve as double function ligand) and aqueous solution of rare earth chloride (0.6ml, 0.5mol/L LnCl
3, Ln:40mol%Gd+45mol%Ce+15mol%Tb) be water, prepared first kind of reverse microemulsion system.With the 40mL normal heptane is oil phase, is tensio-active agent with LAS (0.05M), with Na
3VO
4(0.7ml 0.5mol/L) is water to the aqueous solution, has prepared second kind of reverse microemulsion system.Two kinds of reverse microemulsion systems stir about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, and stir about 20min.Mixture is transferred to the 100mL water heating kettle, and encapsulation is at 100 ℃ of hydrothermal treatment consists 30h.Behind the naturally cooling, add the proper amount of acetone breakdown of emulsion, and more at a high speed (12,000rpm) centrifugal 20min.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed the impurity of absorption several times again.The vacuum-drying precipitation obtains amphipathic GdVO
4: 45mol%Ce, 15mol%Tb nano particle.Under the exciting of 260nm UV-light, this material presents the feature emission of Tb in water.
The amphipathic GdF of embodiment 7 preparations
3: 10mol%Yb, 1mol%Tm nano particle
With the 40mL normal heptane is oil phase, is tensio-active agent with SDS (0.15M), with HOOC-(CH
2)
6-COOH the aqueous solution (0.5mL, 0.5mol/L serve as double function ligand) and aqueous solution of rare earth chloride (0.3ml, 0.01mol/L LnCl
3, Ln:89mol%Gd+10mol%Yb+1mol%Tm) be water, prepared first kind of reverse microemulsion system.With the 40mL normal heptane is oil phase, is tensio-active agent with SDS (0.15M), with NH
4(0.8ml 0.5mol/L) is water to the F aqueous solution, has prepared second kind of reverse microemulsion system.Two kinds of reverse microemulsion systems stir about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, and stir about 20min.Mixture is transferred to the 100mL water heating kettle, and encapsulation is at 100 ℃ of hydrothermal treatment consists 30h.Behind the naturally cooling, add the proper amount of acetone breakdown of emulsion, and more at a high speed (12,000rpm) centrifugal 60min.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed the impurity of absorption several times again.The vacuum-drying precipitation obtains amphipathic GdF
3: 10mol%Yb, 1mol%Tm nano particle.Under the exciting of 980nm light, this material in water, present Tm on converting characteristic emission.
The amphipathic CeF of embodiment 8 preparations
3: 10mol%Yb, 1mol%Ho nano particle
With the 40mL normal heptane is oil phase, is tensio-active agent with SDS (0.5M), with H
2N-(CH
2)
8-COOH the aqueous solution (0.1mL, 0.005mol/L serve as double function ligand) and aqueous solution of rare earth chloride (0.5ml, 0.001mol/L LnCl
3, Ln:89mol%Ce+10mol%Yb+1mol%Ho) be water, prepared first kind of reverse microemulsion system.With the 40mL normal heptane is oil phase, is tensio-active agent with SDS (0.5M), with NH
4(0.6ml 0.1mol/L) is water to the F aqueous solution, has prepared second kind of reverse microemulsion system.Two kinds of reverse microemulsion systems stir about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, and stir about 20min.Mixture is transferred to the 100mL water heating kettle, and encapsulation is at 250 ℃ of hydrothermal treatment consists 0.5h.Behind the naturally cooling, add the proper amount of acetone breakdown of emulsion, and more at a high speed (12,000rpm) centrifugal 5min.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed the impurity of absorption several times again.The vacuum-drying precipitation obtains amphipathic CeF
3: 10mol%Yb, 1mol%Ho nano particle.Under the exciting of 980nm light, this material in water, present Ho on converting characteristic emission.
The amphipathic YF of embodiment 9 preparations
3: 10mol%Yb, 1mol%Ho nano particle
With the 40mL normal heptane is oil phase, is tensio-active agent with SDS (0.5M), with HS-(CH
2)
10-COOH the aqueous solution (2mL, 0.5mol/L serve as double function ligand) and aqueous solution of rare earth chloride (2ml, 0.1mol/L LnCl
3, Ln:89mol%Y+10mol%Yb+1mol%Ho) be water, prepared first kind of reverse microemulsion system.With the 40mL normal heptane is oil phase, is tensio-active agent with SDS (0.5M), with NH
4(4ml 0.6mol/L) is water to the F aqueous solution, has prepared second kind of reverse microemulsion system.Two kinds of reverse microemulsion systems stir about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, and stir about 60min.Mixture is transferred to the 100mL water heating kettle, and encapsulation is at 180 ℃ of hydrothermal treatment consists 10h.Behind the naturally cooling, add the proper amount of acetone breakdown of emulsion, and more at a high speed (12,000rpm) centrifugal 20min.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed the impurity of absorption several times again.The vacuum-drying precipitation obtains amphipathic YF
3: 10mol%Yb, 1mol%Ho nano particle.Under the exciting of 980nm light, this material in water, present Ho on converting characteristic emission.
The amphipathic YF of embodiment 10 preparations
3: 10mol%Yb, 1mol%Ho nano particle
With the 40mL normal heptane is oil phase, is tensio-active agent with SDS (0.5M), with HS-(CH
2)
10-COOH the aqueous solution (0.05mL, 0.5mol/L serve as double function ligand) and aqueous solution of rare earth chloride (0.05ml, 0.1mol/L LnCl
3, Ln:89mol%Y+10mol%Yb+1mol%Ho) be water, prepared first kind of reverse microemulsion system.With the 40mL normal heptane is oil phase, is tensio-active agent with SDS (0.5M), with NH
4(0.1ml 0.6mol/L) is water to the F aqueous solution, has prepared second kind of reverse microemulsion system.Two kinds of reverse microemulsion systems stir about 1h respectively, obtain very limpid colourless solution, subsequently they are mixed, and stir about 5min.Mixture is transferred to the 100mL water heating kettle, and encapsulation is at 180 ℃ of hydrothermal treatment consists 10h.Behind the naturally cooling, add the proper amount of acetone breakdown of emulsion, and more at a high speed (12,000rpm) centrifugal 20min.With normal heptane and ethanol washing and precipitating successively, high speed centrifugation is removed the impurity of absorption several times again.The vacuum-drying precipitation obtains amphipathic YF
3: 10mol%Yb, 1mol%Ho nano particle.Under the exciting of 980nm light, this material in water, present Ho on converting characteristic emission.
Claims (3)
1. the hydro-thermal synthesis process of microemulsion of an amphipathic rare-earth nano material is characterized in that concrete steps are as follows:
(1) preparation reverse microemulsion liquid system
With the 0.001-0.5 mol rare earth compound aqueous solution and 0.001-0.5 mol double function ligand aqueous solution, wherein two kinds of aqueous solution volumes add up to the 0.1-4 milliliter, and the mol ratio between rare earth compound and the double function ligand is 1: 1～1: 10; Being water with this mixed aqueous solution then, is oil phase with 10-100 milliliter non-polar organic solvent, adds first kind of reverse microemulsion liquid system of tensio-active agent preparation; Being water with the fluorochemical of 0.1-8 milliliter 0.001-1 mol or phosphoric acid salt or the vanadate aqueous solution again, is oil phase with 10-100 milliliter non-polar organic solvent, adds second kind of reverse microemulsion liquid system of tensio-active agent preparation; The mol ratio of water and tensio-active agent is 1-80 in two kinds of reverse microemulsion liquid system; Two kinds of reverse microemulsion liquid system stirred respectively 0.1-5 hour, obtained limpid colourless liquid;
(2) hydro-thermal reaction prepares rare earth nano material
Two kinds of reverse micro emulsions that step (1) is obtained mix, stir after 5-60 minute, mixing solutions is transferred to water heating kettle, encapsulation, 100-250 ℃ of hydrothermal treatment consists 0.5～30 hour, behind the naturally cooling, add the acetone breakdown of emulsion, high speed centrifugation 5-60 minute again, with normal heptane and ethanol washing and precipitating successively, high speed centrifugation again, after removing adsorbed organic matter, the vacuum-drying precipitation promptly obtains amphipathic rare earth nano material;
Wherein,
Described non-polar organic solvent is normal hexane, normal heptane, octane-iso, toluene or benzene;
Described double function ligand is X-(CH
2)
n-Y, wherein radicals X be-COOH ,-SH ,-NH
2Perhaps-OH; Group Y is-COOH ,-SH ,-NH
2Perhaps-OH; N is the natural number of 1-30;
Described tensio-active agent is succsinic acid two (2-ethylhexyl) ester sodium sulfonate, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate salt.
2. hydro-thermal synthesis process of microemulsion according to claim 1, it is characterized in that described rare earth compound is the muriate or the nitrate of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium, or wherein several mixtures.
3. hydro-thermal synthesis process of microemulsion according to claim 1 is characterized in that described fluorochemical or phosphoric acid salt or vanadate are respectively their sodium salt, sylvite or ammonium salt.
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| RU2566790C1 (en) * | 2014-07-22 | 2015-10-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Национальный минерально-сырьевой университет "Горный" | Method of praseodymium (iii) salts extraction |
| CN106867305B (en) * | 2017-02-27 | 2017-11-28 | 华中科技大学 | The CeO that a kind of surface is modified2Nano material and product |
| CN108033477B (en) * | 2017-12-12 | 2019-10-15 | 景德镇陶瓷大学 | A kind of magnesium aluminate spinel coated γ ~ Ce2S3Red colorant and preparation method thereof |
| CN109133142B (en) * | 2018-09-28 | 2020-07-21 | 中国恩菲工程技术有限公司 | Preparation method of ultramicro scandium oxide |
| CN109319821A (en) * | 2018-10-31 | 2019-02-12 | 南京科技职业学院 | A kind of preparation method of hydrophily rare earth nano material |
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| CN101100604A (en) * | 2006-07-07 | 2008-01-09 | 中国科学院长春光学精密机械与物理研究所 | Silicon dioxide coating rare earth core-shell upper conversion fluorescence nano-tube and preparation method thereof |
| CN101121543A (en) * | 2007-08-02 | 2008-02-13 | 复旦大学 | Process for preparing water-soluble rare earth nano material |
| CN101177610A (en) * | 2007-11-29 | 2008-05-14 | 东华大学 | Method for preparing nano-grade NaYF4 up-conversion fluorescence host material under normal temperature |
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