CN101914382B - Method for preparing water-soluble and surface-functionalized rare earth nanometer material - Google Patents
Method for preparing water-soluble and surface-functionalized rare earth nanometer material Download PDFInfo
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Abstract
The invention belongs to the field of nanometer material technology and specifically relates to a method for preparing a water-soluble and surface-functionalized rare earth nanometer material. The method comprises the following steps of: heating the rare earth ions and anions to 120 DEG C to 220 DEG C under the protection of an inert gas in polyalcohol as solvent; keeping stirring for 2 to 6 hours to obtain the rare earth nanoparticles, wherein the total mole number of the anion ligand and the rare earth ions is 0.5 to 20 mmol, and the moral ratio is 0.5 to 10; adding surface-functionalization ligand salt into the polyalcohol system, wherein the molar ratio of the surface-functionalization ligand to the rare earth ions is between 0.1 and 20; keeping stirring for 0.5 to 10 hours at the temperature of between 100 DEG C and 220 DEG C under the protection of the inert gas; after the reaction is finished, performing high-speed centrifugation for 2 to 20 minutes and cleaning the deposit with ethanol and water in turn to obtain the water-soluble and surface-functionalized rare earth nanometer material. The method has the advantages of simple production process, wide application range, high reaction yield and low cost.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of preparation method of water-soluble and surface-functionalized rare earth nano material.
Background technology
Rare earth nano material is widely used in a lot of fields.Rare earth luminous nano material has the advantages such as emission is narrow, life-span length, bleach-resistant, so that rare earth nano material is having major application to be worth aspect biomarker and the bio-imaging.The main prerequisite of its biologic applications is: have necessarily water-soluble, and its surface have active group (as-COOH ,-NH
2Perhaps-SH), can be connected with biologically functional molecule.
At present, the method for preparing rare earth nano material has Pintsch process, hydro-thermal (solution heat) method etc., but the rare earth nano material periphery that these methods make is alkyl chain, so they generally are hydrophobic, can only be dissolved in non-polar organic solvent, also be difficult to further functionalization.Current improvement strategy commonly used has surface ligand oxidation style, surface parcel one deck SiO
2Perhaps macromolecular material, layer assembly etc., these complex process, costs that improve the synthetic rare earth nano material of water miscible method are high.The present invention relates to the preparation method of a kind of one kettle way synthesizing water-solubility and surface-functionalized rare earth nano material.Present method production technique is simple, and use range is extensive, and reaction yield is high, and is with low cost.
Summary of the invention
The object of the present invention is to provide a kind of general preparation method of water miscible and surface-functionalized rare earth nano material.
The concrete technology step of the inventive method is as follows: under heating (50~100 ℃) backflow and continuous agitation condition; anion ligand and rare earth ion are dissolved in respectively in 5~50mL polyvalent alcohol; total mole number 0.5~the 20mmol of anion ligand and rare earth ion; mol ratio is 0.5~10; vigorous stirring obtains clear soln; then under the condition that constantly stirs; the polyhydric alcohol solutions that is dispersed with rare earth ion is mixed with the polyhydric alcohol solutions that is dispersed with anion ligand; under protection of inert gas, be heated to 120~220 ℃, keep stirring 2~6 hours.
Reaction is cooled to 25~100 ℃ after finishing, and surface-functionalized part salt is joined in the above-mentioned system, and the mol ratio of surface-functionalized part and rare earth ion is 0.1~20.Keep stirring 0.5~10 hour in 100~220 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 2~20 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, vacuum-drying precipitates and obtains required rare earth nano material sample.The surface of rare earth nano material is polyvalent alcohol and functionalized ligand, causes rare earth nano material to have water-soluble and the function of surface active group.
The rare earth ion that uses among the present invention is muriate or the nitrate of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and yttrium (Y); Or their mixture.
Use anion ligand to be fluorochemical, cation fluorine compound composite salt (Na, K or NH among the present invention
4Salt), negatively charged ion fluorochemical composite salt (OF or (OH) CO
3Salt), oxyhydroxide, oxide compound, composite oxides, carbonate, titanate, borate, phosphoric acid salt, tungstate or vanadate.
The polyvalent alcohol that uses among the present invention typically has glycol ether, ethylene glycol, glycerol.
The surface-functionalized part that uses among the present invention is alkyl chain carboxylic acid or polymkeric substance or organic molecule, and alkyl chain carboxylic acid and polymkeric substance require the one end to contain carboxylic group, and the other end contains the groups such as amino, carboxyl, maleimide, aldehyde radical or hydroxyl; Organic molecule requires to contain at least in the molecular structure carboxylic group.This functional ligand can be water miscible, also can be oil-soluble.
The surface-functionalized part that uses among the present invention comprises: the two carboxylic acids of aminoundecanoic acid, 6-aminocaprolc acid, polyoxyethylene glycol, folic acid, N-caproic acid-4-horse quinoline base-1, the acid of 8-naphthalene acid anhydride, two-(2-phenylpyridine)-2-(4-carboxyl pyridine) γ-picolinic acid close iridium, L-Histidine, hexanodioic acid, nonane diacid, pentanedioic acid and the 4-(4-(2-(phenylformic acid of 5-chloro-2-methyl thiophene-3-)-cyclopentenes-1-)-5-thiotolene-2-).
Preparation method's cost of the present invention is low, easy, general, and the rare earth nano material of preparation has good water-soluble, and there is active group on its surface, and the active group kind depends on the function of surface part of adding.
Description of drawings
Fig. 1 is the surface-functionalized NaYF of aminoundecanoic acid
4The infrared spectra of nano material.
Fig. 2 is the surface-functionalized NaYF of aminoundecanoic acid
4The nuclear-magnetism spectrum of nano material.
Fig. 3 is the surface-functionalized CeF of 6-aminocaprolc acid
3: the emmission spectrum of 10mol%Tb nano material.
Fig. 4 is the two surface-functionalized LaPO of carboxylic acid of polyoxyethylene glycol
4: 20mol%Yb, the infrared spectra of 2mol%Er nano particle.
Fig. 5 is the two surface-functionalized LaPO of carboxylic acid of polyoxyethylene glycol
4: 20mol%Yb, the nuclear-magnetism spectrum of 2mol%Er nano particle.
Fig. 6 is the surface-functionalized Gd of folic acid
2O
3: the infrared spectra of 10mol%Eu nano particle.
Fig. 7 is the surface-functionalized Gd of folic acid
2O
3: the nuclear-magnetism spectrum of 10mol%Eu nano particle.
Fig. 8 is N-caproic acid-4-horse quinoline base-1, the YVO of 8-naphthalene acid anhydride acid surfaces functionalization
4The emmission spectrum of nano particle.
Fig. 9 is the surface-functionalized LaWO of pentanedioic acid
3: 20mol%Yb, the emmission spectrum of 2mol%Er nano particle.
Figure 10 is that two-(2-phenylpyridine)-2-(4-carboxyl pyridine) γ-picolinic acid closes the surface-functionalized Tm of iridium
2(CO
3)
3The infrared spectra of nano particle.
Figure 11 is the surface-functionalized NdTiO of L-Histidine
3The nuclear-magnetism spectrum of nano particle.
Embodiment
The invention will be further described by the following examples, but the present invention is not constituted any limitation.
The surface-functionalized NaYF of embodiment 1 preparation aminoundecanoic acid
4Nano material
Under 100 ℃ of backflows of heating and continuous agitation condition, 2mmol NaF is dissolved in the glycol ether of 15mL, simultaneously with 0.5mmol YCl
3Be dissolved in the 15mL glycol ether, vigorous stirring obtains clear soln again.Then under the condition that constantly stirs, will be dispersed with YCl
3Glycol ether solution and the glycol ether solution that is dispersed with NaF mix, under protection of inert gas, be heated to 200 ℃, keep stirring 2 hours.
Reaction is cooled to 100 ℃ after finishing, and 4mmol aminoundecanoic acid sodium joins in the above-mentioned system, keeps stirring 4 hours in 160 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 8 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, vacuum-drying precipitates and obtains required rare earth nano material sample.Fig. 1 is the surface-functionalized NaYF of aminoundecanoic acid
4The infrared spectra of nano material, Fig. 2 are the surface-functionalized NaYF of aminoundecanoic acid
4The nuclear-magnetism spectrum of nano material.Fig. 1 result shows, nano material is 2928 and 2855cm
-1There is absorbing surface at the place, corresponding to long alkyl chain-CH
2Symmetry and asymmetric stretching vibration.1567cm
-1The place points out absorption into the one-level ammonium, and 1459 and 1411cm
-1The place is corresponding to the stretching vibration of carboxyl and C-C.Mr peak position and the aminoundecanoic acid of Fig. 2 match.Infrared and nuclear-magnetism result shows that all aminoundecanoic acid and glycol ether are as being total to the particle surface of part at rare earth nano.
The surface-functionalized CeF of embodiment 2 preparation 6-aminocaprolc acids
3: the 10mol%Tb nano material
Under 70 ℃ of backflows of heating and continuous agitation condition, with 2.5mmol NH
4F is dissolved in the glycerol of 20mL, is 1mmol (90mol%CeCl with total mole simultaneously
3, 10mol%CeCl
3) the rare earth hybrid ionic is dissolved in the 15mL glycerol again, vigorous stirring obtains clear soln.Then under the condition that constantly stirs, will be dispersed with the glycerol solution of rare earth hybrid ionic and be dispersed with NH
4The glycerol solution of F mixes, and is heated to 180 ℃ under protection of inert gas, keeps stirring 4 hours.
Reaction is cooled to 25 ℃ after finishing, and 2mmol 6-aminocaprolc acid sodium joins in the above-mentioned system, keeps stirring 1 hour in 220 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 10 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, vacuum-drying precipitates and obtains required rare earth nano material sample.Fig. 3 is presented at 254nm and excites down, the CeF that 6-aminocaprolc acid is surface-functionalized
3: the fluorescence spectrum of 10mol%Tb nano material.This material also presents the characteristic emission of typical 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 two surface-functionalized LaPO of carboxylic acid of embodiment 3 preparation polyoxyethylene glycol
4: 20mol%Yb, 2mol%Er nano particle
Under 90 ℃ of backflows of heating and continuous agitation condition, with 1.8mmol (NH
4)
3PO
4Being dissolved in the glycol ether of 15mL, is 1mmol (78mol%LaCl with total mole simultaneously
3, 20mol%CeCl
3, 2mol%TbCl
3) the rare earth hybrid ionic is dissolved in the 20mL glycol ether again, vigorous stirring obtains clear soln.Then under the condition that constantly stirs, will be dispersed with the glycol ether solution of rare earth hybrid ionic and be dispersed with (NH
4)
3PO
4Glycol ether solution mix, under protection of inert gas, be heated to 180 ℃, keep stirring 4 hours.
Reaction is cooled to 25 ℃ after finishing, and the two carboxylic acid sodium salts (molecular weight is 600g/mol) of 1mmol polyoxyethylene glycol join in the above-mentioned system, keep stirring 0.5 hour in 170 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 7 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, vacuum-drying precipitates and obtains required rare earth nano material sample.Fig. 4 shows the two surface-functionalized LaPO of carboxylic acid of polyoxyethylene glycol
4: 20mol%Yb, the INFRARED SPECTRUM of 2mol%Er nano particle, 2928 and 2858cm
-1The place shows the two carboxylic acid long alkyl chain-CH of polyoxyethylene glycol
2Symmetry and asymmetric stretching vibration.1627cm
-1Asymmetrical stretching vibration corresponding to the two carboxyls of polyoxyethylene glycol.Fig. 5 shows the two surface-functionalized LaPO of carboxylic acid of polyoxyethylene glycol
4: 20mol%Yb, the nuclear-magnetism of 2mol%Er nano particle spectrum, 3.87ppm point out into be connected with the two carboxylic acids of polyoxyethylene glycol-CH
2-the peak.Infrared all showing with the nuclear-magnetism result obtained the two surface-functionalized nano particles of carboxylic acid of polyoxyethylene glycol.
The surface-functionalized Gd of embodiment 4 preparation folic acid
2O
3: the 10mol%Eu nano particle
Under 50 ℃ of backflows of heating and continuous agitation condition, 1.5mmol NaOH is dissolved in the glycol ether of 20mL, be 1mmol (90mol%GdCl with total mole simultaneously
3, 10mol%EuCl
3) the rare earth hybrid ionic is dissolved in the 12mL glycol ether again, vigorous stirring obtains clear soln.Then under the condition that constantly stirs, the glycol ether solution that is dispersed with the rare earth hybrid ionic is mixed with the glycol ether solution that is dispersed with NaOH, under protection of inert gas, be heated to 210 ℃, keep stirring 2.5 hours.
Reaction is cooled to 80 ℃ after finishing, and 0.5mmol folic acid sodium salt joins in the above-mentioned system, keeps stirring 3 hours in 210 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 20 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, vacuum-drying precipitates and obtains required rare earth nano material sample.Fig. 6 shows the Gd that folic acid is surface-functionalized
2O
3: 10mol%Eu, the INFRARED SPECTRUM of nano particle, 1592,1554,1346 and 1178cm
-1The place shows the characteristic peak of folic acid phenyl ring.Fig. 7 shows the Gd that folic acid is surface-functionalized
2O
3: the nuclear-magnetism spectrum of 10mol%Eu nano particle, the peak of nuclear-magnetism spectrum and the characteristic peak of folic acid all mate.Infrared all showing with the nuclear-magnetism result obtained the surface-functionalized nano particle of folic acid.
Under 90 ℃ of backflows of heating and continuous agitation condition, with 2mmol (NH
4)
3VO
4Be dissolved in the ethylene glycol of 15mL, simultaneously with 1mmol YCl
3The rare earth hybrid ionic is dissolved in the 12mL ethylene glycol again, and vigorous stirring obtains clear soln.Then under the condition that constantly stirs, will be dispersed with the ethylene glycol solution of rare earth hybrid ionic and be dispersed with (NH
4)
3VO
4Ethylene glycol solution mix, under protection of inert gas, be heated to 150 ℃, keep stirring 3 hours.
Reaction is cooled to 25 ℃ after finishing, 0.5mmol N-caproic acid-4-horse quinoline base-1, and 8-naphthalene acid anhydride acid sodium-salt joins in the above-mentioned system, keeps stirring 0.5 hour in 200 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 15 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, vacuum-drying precipitates and obtains required rare earth nano material sample.Fig. 8 shows N-caproic acid-4-horse quinoline base-1, the YVO of 8-naphthalene acid anhydride acid surfaces functionalization
4The characteristic emission spectrum of nano particle.Proof has obtained N-caproic acid-4-horse quinoline base-1, the rare-earth nanometer particles of 8-naphthalene acid anhydride acid surfaces functionalization.
The surface-functionalized LaWO of embodiment 6 preparation pentanedioic acids
3: 20mol%Yb, 2mol%Er nano particle
Under 45 ℃ of backflows of heating and continuous agitation condition, with 1mmol (NH
4)
3WO
3Being dissolved in the glycerol of 14mL, is 1mmol (80mol%LaCl with total mole simultaneously
3, 18mol%YbCl
3, 2mol%ErCl
3) the rare earth hybrid ionic is dissolved in the 16mL glycerol again, vigorous stirring obtains clear soln.Then under the condition that constantly stirs, will be dispersed with the glycerol solution of rare earth hybrid ionic and be dispersed with (NH
4)
3WO
3Glycerol solution mix, under protection of inert gas, be heated to 170 ℃, keep stirring 2.5 hours.
Reaction is cooled to 80 ℃ after finishing, and 1.5mmol pentanedioic acid sodium salt joins in the above-mentioned system, keeps stirring 2.5 hours in 150 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 7 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, vacuum-drying precipitates and obtains required rare earth nano material sample.The La WO that pentanedioic acid is surface-functionalized
3: 20mol%Yb, 2mol%Er nano particle in water, present typical green glow (525~555nm) and ruddiness (635~660nm) upper switching emission, its result such as Fig. 9 have shown that this material has good upper conversion performance.
Under 50 ℃ of heating and continuous agitation condition, with 2.6mmol Na
2CO
3Be dissolved in the glycol ether of 15mL, simultaneously with 0.66mmol TmCl
3Be dissolved in the 15mL glycol ether.Then under the condition that constantly stirs, with TmCl
3Glycol ether solution and Na
2CO
3Glycol ether solution mix, under protection of inert gas, be heated to 200 ℃, keep stirring 3 hours.
Reaction is cooled to 25 ℃ after finishing, and 0.05mmol two-(2-phenylpyridine)-2-(4-carboxyl pyridine) γ-picolinic acid closes the iridium ammonium salt and joins in the above-mentioned system, keeps stirring 3 hours in 100 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 8 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, and the vacuum-drying precipitation obtains required rare earth nano material sample.Figure 10 is the surface-functionalized Tm of complex of iridium of two carboxylic acid functional parts
2(CO
3)
3The infrared spectra of nano particle has phenyl ring, pyridine ring, carboxylic acid functional in the complex of iridium.
The surface-functionalized NdTiO of embodiment 8 preparation L-Histidines
3Nano particle
Under 100 ℃ of heating and continuous agitation condition, with 3mmol (NH
4)
3TiO
3Be dissolved in the glycol ether of 15mL, with 1mmol NdCl
3Be dissolved in the 20mL glycol ether.Then under the condition that constantly stirs, with NdCl
3Glycol ether solution and (NH
4)
3TiO
3Glycol ether solution mix, under protection of inert gas, be heated to 170 ℃, keep stirring 2.5 hours.
Reaction is cooled to 50 ℃ after finishing, and 0.1mmol L-Histidine sodium salt joins in the above-mentioned system, keeps stirring 9.5 hours in 110 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 8 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, and the vacuum-drying precipitation obtains required rare earth nano material sample.The NdTiO that Figure 11 L-Histidine is surface-functionalized
3The nuclear-magnetism of nano particle spectrum, corresponding Histidine imidazoles ring hydrogen.
The surface-functionalized PrBO of embodiment 9 preparation hexanodioic acids
3Nano particle
Under 100 ℃ of heating and continuous agitation condition, with 1.2mmol (NH
4)
3BO
3Be dissolved in the glycerol of 35mL, with 1.5mmol PrCl
3Be dissolved in the 20mL glycerol.Then under the condition that constantly stirs, with PrCl
3Glycerol solution and (NH
4)
3BO
3Glycerol solution mix, under protection of inert gas, be heated to 175 ℃, keep stirring 3 hours.
Reaction is cooled to 70 ℃ after finishing, and 0.2mmol hexanodioic acid sodium salt joins in the above-mentioned system, keeps stirring 10 hours in 120 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 2 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, and the vacuum-drying precipitation obtains required rare earth nano material sample.
Surface-functionalized Sm (OH) CO of embodiment 10 preparation nonane diacids
3Nano particle
Under 70 ℃ of heating and continuous agitation condition, with 1mmol NaOH and 1mmol Na
2CO
3Be dissolved in the ethylene glycol of 12mL, with 1mmol SmCl
3Be dissolved in the 30mL ethylene glycol.Then under the condition that constantly stirs, with SmCl
3Ethylene glycol solution and NaOH and Na
2CO
3Ethylene glycol solution mix, under protection of inert gas, be heated to 200 ℃, keep stirring 4 hours.
Reaction is cooled to 50 ℃ after finishing, and 20mmol nonane diacid sodium salt joins in the above-mentioned system, keeps stirring 4 hours in 180 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 4 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, and the vacuum-drying precipitation obtains required rare earth nano material sample.
Embodiment 11 preparation 4-(4-(2-(the surface-functionalized Eu (OH) of phenylformic acid of 5-chloro-2-methyl thiophene-3-)-cyclopentenes-1-)-5-thiotolene-2-)
3Nano particle
Under 70 ℃ of heating and continuous agitation condition, 5mmolNaOH is dissolved in the glycol ether of 12mL, with 15mmol EuCl
3Be dissolved in the 22mL glycol ether.Then under the condition that constantly stirs, with EuCl
3Glycol ether solution and the glycol ether solution of NaOH mix, under protection of inert gas, be heated to 200 ℃, keep stirring 4 hours.
After reaction finishes; be cooled to 100 ℃; 1.5mmol 4-(4-(2-(5-chloro-2-methyl thiophene-3-)-cyclopentenes-1-)-the 5-thiotolene-2-) the phenylformic acid sodium salt joins in the above-mentioned system, keeps stirring 3 hours in 150 ℃ under the protection of inert gas.After reaction finishes, naturally cooling, high speed centrifugation is 6 minutes again, and with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, and the vacuum-drying precipitation obtains required rare earth nano material sample.
Claims (6)
1. the preparation method of a water-soluble and surface-functionalized rare earth nano material is characterized in that the preparation method is specially:
Under 50~100 ℃ of reflux and continuous agitation condition, anion ligand and rare earth compound are dissolved in respectively in 5~50mL polyvalent alcohol, total mole number 0.5~the 20mmol of anion ligand and rare earth ion, mol ratio is 0.5~10, vigorous stirring obtains clear soln, then under the condition that constantly stirs, the polyhydric alcohol solutions that is dispersed with rare earth ion is mixed with the polyhydric alcohol solutions that is dispersed with anion ligand, under protection of inert gas, be heated to 120~220 ℃, keep stirring 2~6 hours, after reaction finishes, be cooled to 25~100 ℃, surface-functionalized part salt is joined in the above-mentioned system, the mol ratio of surface-functionalized part and rare earth ion is 0.1~20, keep stirring 0.5~10 hour in 100~220 ℃ under the protection of inert gas, after reaction finishes, naturally cooling, high speed centrifugation is 2~20 minutes again, with second alcohol and water successively washing and precipitating, high speed centrifugation is removed the organism of absorption several times again, and the vacuum-drying precipitation makes required rare earth nano material sample;
Wherein,
Described anion ligand is fluorochemical, cation fluorine compound composite salt, negatively charged ion fluorochemical composite salt, oxyhydroxide, sulfide, oxide compound, composite oxides, carbonate, titanate, borate, phosphoric acid salt, tungstate or vanadate;
Described surface-functionalized part is alkyl chain carboxylic acid or polymkeric substance or organic molecule, and alkyl chain carboxylic acid and polymkeric substance require the one end to contain carboxylic group, and the other end contains amino, carboxyl, maleimide, aldehyde radical or oh group; Organic molecule requires to contain at least in the molecular structure carboxylic group, and this functional ligand can be water miscible, also can be oil-soluble.
2. the preparation method of rare earth nano material according to claim 1 is characterized in that rare earth compound is muriate or the nitrate of lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, scandium Sc and yttrium Y; Or their mixture.
3. the preparation method of rare earth nano material according to claim 1 is characterized in that the polyvalent alcohol that uses comprises glycol ether, ethylene glycol and glycerol.
4. the preparation method of rare earth nano material according to claim 1, it is characterized in that described surface-functionalized part comprises: the two carboxylic acids of aminoundecanoic acid, 6-aminocaprolc acid, polyoxyethylene glycol, folic acid, N-caproic acid-4-horse quinoline base-1, the acid of 8-naphthalene acid anhydride, two-(2-phenylpyridine)-2-(4-carboxyl pyridine) γ-picolinic acid close iridium, L-Histidine, hexanodioic acid, nonane diacid, pentanedioic acid and the 4-(4-(2-(phenylformic acid of 5-chloro-2-methyl thiophene-3-)-cyclopentenes-1-)-5-thiotolene-2-).
5. the preparation method of rare earth nano material according to claim 1 is characterized in that described cation fluorine compound composite salt is sodium salt, sylvite or ammonium salt.
6. the preparation method of rare earth nano material according to claim 1 is characterized in that described negatively charged ion fluorochemical composite salt is OF salt.
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CN104591253B (en) * | 2015-02-02 | 2016-08-17 | 首都师范大学 | A kind of method for synthesis of microemulsion of porous water-solubility rare-earth nano material |
CN104910915A (en) * | 2015-04-22 | 2015-09-16 | 南京工业大学 | Preparation method and application of hydrophilic rare earth nano-material |
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 |
CN111995759B (en) * | 2020-02-15 | 2023-03-14 | 江西师范大学 | Rare earth-folic acid coordination polymer nano particle and preparation method thereof |
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CN101241788A (en) * | 2007-01-15 | 2008-08-13 | 中国科学院化学研究所 | Biological compatibility magnetic nano crystal for high dissolving and stable distribution in physiologicalbuffer liquid and its making method |
CN101289216A (en) * | 2008-06-05 | 2008-10-22 | 复旦大学 | Method for synthesizing microemulsion of water-solubility rare-earth nano material |
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胡鹤.稀土上转换发光纳米材料的制备及其在生物医学成像中的应用.《中国博士学位论文全文数据库·工程科技I辑》.2010,B020-21. |
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