CN105505392B - Rare earth oxyfluoride nano material and its preparation method and application - Google Patents
Rare earth oxyfluoride nano material and its preparation method and application Download PDFInfo
- Publication number
- CN105505392B CN105505392B CN201510903999.5A CN201510903999A CN105505392B CN 105505392 B CN105505392 B CN 105505392B CN 201510903999 A CN201510903999 A CN 201510903999A CN 105505392 B CN105505392 B CN 105505392B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- preparation
- nano material
- nanocrystalline
- earth oxyfluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
- C09K11/7788—Oxyhalogenides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
- C09K11/777—Oxyhalogenides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
The present invention relates to a kind of rare earth oxyfluoride nano material and its preparation method and application.This method uses rare earth trifluoroacetate and ammonium acetate as presoma, and utilizes high-temperature solvent thermal decomposition method, so as to obtain oil-soluble rare earth oxyfluoride nano material.The synthesis condition is easily controlled, reproducible, and the nano material prepared is in granular form, and the dispersiveness of particle, homogeneity and repeatability are all fine.Rare earth oxyfluoride nano material prepared by the present invention is a kind of preferable host material that can be applied to biological detection and bio-imaging field.
Description
Technical field
The invention belongs to nano meter biomaterial technical field, more particularly, to a kind of rare earth oxyfluoride nano material and its
Preparation method and application.
Background technology
Rear-earth-doped phosphor obtains extensive concern in recent years, and these materials are shown in 3 D stereo, false proof skill
Art, solid-state laser, optical storage, solar cell etc. all embody great application value, wherein most noticeable
It is application of the rear-earth-doped inorganic nano material risen recently in terms of fluorescent biolabels.With traditional fluorescence labeling material
Compared with (such as fluorescent dye is with quantum dot), rear-earth-doped inorganic nano material has high thermal stability, long fluorescence lifetime, low toxicity
Property, the comprehensive advantage such as tunable fluorescence emission wavelengths, be universal good fluorescent biolabels material of new generation at present.
Fluorescent biolabels material suffers from pole to the luminous of nano particle, size, water solubility and biocompatibility etc.
High requirement.Wherein, physical and chemical performance and the direct phase of selected host material such as the luminous of nano particle, biocompatibility
Close.Rare earth oxyfluoride host material inherit fluoride relative to oxide phonon energy it is low the advantages of, and compared to fluorine
Compound has more preferable mechanical performance and thermal stability.In other words, oxyfluoride has the advantages of fluoride and oxide concurrently, is
A kind of good host material.It is worth noting that, in rare earth oxyfluoride in this kind of material, fluorine luteium oxide (such as Lu6O5F8)
Because of its special architectural feature, make it have than fluoride (such as NaEuF4) much higher mass density and rare earth ion mole it is close
Degree, and the coordination environment of fluorine luteium oxide Rare Earth Ion is complicated, and Local Symmetry is relatively low, is advantageous to improve doping with rare-earth ions
Between resonant energy transfer efficiency and centre of luminescence electron transition probability.
Due to the limitation of existing synthetic method, the report of the homogeneous rare earth oxyfluoride nano material of synthesis single dispersing, pattern
Road is less so far.At present, synthesize the homogeneous rare earth oxyfluoride nano material of single dispersing, pattern and mainly pass through rare earth trifluoroacetic acid
Method (the bibliography that the single presoma of salt is thermally decomposed in high-temperature solvent：Yan Chunhua et al.,From
Trifluoroacetate Complex Precursors to Monodisperse Rare-Earth Fluoride and
Oxyfluoride Nanocrystals with Diverse Shapes through Controlled Fluorination
in Solution Phase,Chem.Eur.J.,13,2320-2332(2007)).However, this method is needed by finely adjusting
Fluorination and the fluorine oxidizing process of solvent burden ratio and controlling reaction temperature rare earth ion are controlled, namely its reaction condition variable range is very
It is narrow, and easily occur fluoride dephasign in synthetic product.
In addition, the research for being related to rare earth oxyfluoride material before is mainly also focused in luminescent properties research, need out
The application field for sending out brand-new.
The content of the invention
The purpose of the present invention aims to provide a kind of rare earth oxyfluoride nano material and its preparation method and application, the preparation
The synthesis condition of method is easily controlled, and the modified water-soluble fluorine oxide-based nanomaterial of the oil-soluble and surface prepared is in
Granular, the dispersiveness of the particle, homogeneity and repeatability are all fine, and the rare earth oxyfluoride nano material can be used for giving birth to
Thing field, in terms of being particularly applied to fluorescence-labeled bio detection and bio-imaging.
To achieve these goals, according to an aspect of the invention, there is provided a kind of rare earth oxyfluoride nano material
Preparation method, it uses rare earth trifluoroacetate and ammonium acetate as presoma, and utilizes high-temperature solvent thermal decomposition method, so as to
Obtain oil-soluble rare earth oxyfluoride nano material.
It is above-mentioned to prepare oil-soluble rare earth oxyfluoride nano material using high-temperature solvent thermal decomposition method according to the present invention
Step includes：
S1, rare earth trifluoroacetate and ammonium acetate are weighed at room temperature, solvent is added into the mixture of the two, consolidate
Body mixed solution；
S2, solid mixed solution is heated and is incubated under inert gas shielding, so that the reaction in solid mixed solution
Thing dissolves；
S3, continue to heat under inert gas shielding and be incubated, be cooled to room temperature, centrifuge, wash, dry, obtain
The oil-soluble rare earth oxyfluoride nano material.
According to the present invention, solid mixed solution is heated to 100~130 DEG C and 20~30 points of insulation in step S2
Clock, so that the reactant dissolving in solid mixed solution.
According to the present invention, 280~330 DEG C are heated in step S3 and is incubated 1~2 hour.
According to the present invention, in above-mentioned preparation method, the mol ratio of rare earth trifluoroacetate and ammonium acetate is 1:(1~1.5).
According to the present invention, in above-mentioned preparation method, the solvent is the mixed of two or three of oleic acid, oleyl amine and octadecylene
Bonding solvent；It is preferred that the mol ratio of the in the mixed solvent oleic acid, oleyl amine and octadecylene is 1:(1~2):(0~1).
According to the present invention, in above-mentioned preparation method, the rare earth trifluoroacetate be selected from Y, Sc, La, Ce, Pr, Nd, Sm,
One or more in Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu trifluoroacetate.
According to the present invention, above-mentioned preparation method also includes carrying out table to the oil-soluble rare earth oxyfluoride nano material
Face is modified, to obtain the process of water miscible rare earth oxyfluoride nano material.
According to the present invention, the step of oil-soluble rare earth oxyfluoride nano material progress surface modification, is included：
The appropriate oil-soluble rare earth oxyfluoride nano material is taken to be scattered in chloro-carbon solvent (such as chloroform)
In, then it is added dropwise in the solution containing modifying agent, stirring (such as stirring at normal temperature, mixing time are, for example, 12-36 hours,
It is preferred that 12 hours), stratification, take upper strata aqueous phase solution to be centrifuged, the solid isolated is scrubbed, after drying, obtains water-soluble
The rare earth oxyfluoride nano material of property.
Specifically, the modifying agent in the solution containing modifying agent can be sodium citrate.Solution is ethanol and citric acid
Volume ratio (the mL of the mixture of sodium water solution (0.1~0.5mol/L, such as 0.2mol/L), ethanol and sodium citrate aqueous solution:
ML it is about) 1:1 (such as 2mL：2mL).It is obtained be water miscible citric acid modification rare earth oxyfluoride it is nanocrystalline.
Present invention also offers a kind of rare earth oxyfluoride nano material prepared by the above method.
According to the present invention, the rare earth oxyfluoride nano material be it is rear-earth-doped or undoped with MOF nano materials, M
For La, Gd or Y.Such as can be MOF:X%Eu is nanocrystalline, wherein, M La, Gd or Y, 0≤x≤50, it is preferred that 0≤x≤
10.Specific for example can be LaOF:5%Eu is nanocrystalline, GdOF:5%Eu is nanocrystalline, YOF:5%Eu is nanocrystalline.
According to the present invention, the rare earth oxyfluoride nano material be it is rear-earth-doped or undoped with Lu6O5F8Nanometer material
Material, such as can be Lu6O5F8:Y%Ln3+It is nanocrystalline, wherein, 0≤y≤50 (preferable, 0≤y≤10), Ln3+Selected from Ce,
One or more in Yb, Er, Tm, Ho, Eu, Gd, Tb, Dy, Sm, Nd and Pr.Such as can be Lu6O5F8:Y%Eu3+Nanometer
Crystalline substance, 0≤y≤50 (preferable, 0≤y≤10)；Specific such as Lu6O5F8:5%Eu is nanocrystalline, Lu6O5F8:40%Eu it is nanocrystalline or
Lu6O5F8It is nanocrystalline.Other for example can be Lu6O5F8:y1%Yb3+/y2%Er3+It is nanocrystalline, 0≤y1+y2≤ 50 (it is preferable, 0
≤y1+y2≤ 30), for example, 10≤y1≤ 30,0≤y2≤10。
According to the present invention, the rare earth oxyfluoride nano material be it is rear-earth-doped or undoped with Eu6O5F8Nanometer material
Material, it for example can be Eu6O5F8:Z%Ln3+It is nanocrystalline, 0≤z≤50 (preferable, 0≤z≤10), Ln3+Selected from Ce, Yb,
One or more in Er, Tm, Ho, Lu, Gd, Tb, Dy, Sm, Nd and Pr.Such as can be Eu6O5F8:Z%Lu3+It is nanocrystalline, 0
≤ z≤50 (preferable, 0≤z≤10)；Specific such as Eu6O5F8:5%Lu is nanocrystalline, Eu6O5F8:40%Lu is nanocrystalline or Eu6O5F8
It is nanocrystalline.Other for example can be Eu6O5F8:z1%Yb3+/z2%Er3+It is nanocrystalline, 0≤z1+z2≤ 50 (preferable, 0≤z1+z2
≤ 30), for example, 10≤z1≤ 30,0≤z2≤10。
Invention further provides a kind of application of above-mentioned rare earth oxyfluoride nano material in biological technical field；
It is preferred that the application in biological detection and bio-imaging.Further preferably, Lu6O5F8:Y%Eu3+Nanocrystalline (0≤y≤50) are applied
In tumor-marker analyte detection.Preferably, Lu6O5F8:Y%Yb3+/Er3+Nanocrystalline (0≤y≤50) are applied to upper conversion imaging, tool
Body is cell imaging.Preferably, Lu6O5F8The nanocrystalline CT that is applied to is imaged, such as can be used as CT contrast agent.Preferably, it is water-soluble
Lu6O5F8:Y%Yb/Er nanocrystalline (0≤y≤50) can apply to cell imaging or CT contrast agent.
The beneficial effects of the present invention are：
1) present invention is synthesized by the use of rare earth trifluoroacetate and ammonium acetate as presoma and high-temperature solvent thermal decomposition method
Series of rare earth oxyfluoride nano material is gone out, the synthetic method condition is easily controlled, reproducible, the rare earth fluorine prepared
Oxide-based nanomaterial is in granular form, and the dispersiveness of particle, homogeneity and repeatability are all fine.
2) due to Lu6O5F8Belong to rhombic system, atomic space bulk density is high in its crystal structure, therefore these are special
Architectural feature cause the rear-earth-doped Lu prepared using the above method6O5F8Nano material have very high mass density and
Rare earth ion molar density.And the coordination environment of fluorine luteium oxide Rare Earth Ion is complicated, and Local Symmetry is relatively low, is advantageous to carry
Resonant energy transfer efficiency and centre of luminescence electron transition probability between highly doped rare earth ion, so that rear-earth-doped
Lu6O5F8Nano material turns into a kind of preferably host material and is applied to biological detection and bio-imaging field.
Brief description of the drawings
That in Fig. 1 a), b), c) and d) is respectively Emission in Cubic LaOF in embodiment 1:X-ray powder nanocrystalline 5%Eu spreads out
Penetrate figure, transmission electron microscope picture, and nanocrystalline lower transfer excitation and emission spectra figure；
That in Fig. 2 a), b), c) and d) is respectively tripartite's phase GdOF in embodiment 1:X-ray powder nanocrystalline 5%Eu spreads out
Penetrate figure, transmission electron microscope picture, and nanocrystalline lower transfer excitation and emission spectra figure；
That in Fig. 3 a), b), c) and d) is respectively Tetragonal YOF in embodiment 1:X-ray powder nanocrystalline 5%Eu spreads out
Penetrate figure, transmission electron microscope picture, and nanocrystalline lower transfer excitation and emission spectra figure；
That in Fig. 4 a), b), c) and d) is respectively orthorhombic phase Lu in embodiment 16O5F8:X-ray powder nanocrystalline 5%Eu
Diffraction pattern, transmission electron microscope picture, and nanocrystalline lower transfer excitation and emission spectra figure；
That in Fig. 5 a), b), c) and d) is respectively orthorhombic phase Eu in embodiment 16O5F8Nanocrystalline X-ray powder diffraction
Figure, transmission electron microscope picture, and nanocrystalline lower transfer excitation and emission spectra figure；
That in Fig. 6 a), b) is respectively orthorhombic phase Lu in embodiment 26O5F8:X-ray powder diffraction figure nanocrystalline 40%Eu
And transmission electron microscope picture；
Fig. 7 is that double-antibody method detects PSA canonical plotting in embodiment 2；
Fig. 8 is orthorhombic phase Lu in embodiment 36O5F8:X-ray powder diffraction figure nanocrystalline Yb/Er and transmission electron microscope picture；
Fig. 9 is orthorhombic phase Lu in embodiment 36O5F8:The nanocrystalline up-conversion fluorescences in the case where 980nm lasers excite of Yb/Er
Spectrogram (INSTRUMENT MODEL FSP920-C, producer Edinburgh)；
Figure 10 is Lu in embodiment 36O5F8:The nanocrystalline biologies to normal human embryonic lung fibroblasts (HELF) of Yb/Er
Security test result (INSTRUMENT MODEL is Synergy 4, producer BioTek)；
Figure 11 is Lu in embodiment 36O5F8:The nanocrystalline upper conversion imaging effects to human lung carcinoma cell (H1299) of Yb/Er
(INSTRUMENT MODEL FV1000, producer Olympus)；
Figure 12 is Lu in embodiment 36O5F8:Yb/Er is nanocrystalline with the CT imaging effects pair of commercialization contrast agent Iopromide
Than scheming (INSTRUMENT MODEL is Inveon MMCT, producer SIEMENS)；
Figure 13 is the rear-earth-doped Lu of the present invention6O5F8The nanocrystalline schematic diagram applied in biological detection and imaging field.
Embodiment
During in order to solve to prepare rare earth oxyfluoride nano material in the prior art, it is necessary to reaction condition is carried out it is fine,
Harsh regulation and control, and easily occur the problem of fluoride dephasign in synthetic product, the invention provides a kind of rare earth oxyfluoride
The preparation method of nano material, it is by the use of rare earth trifluoroacetate and ammonium acetate as presoma, utilizes high-temperature solvent heat point
Solution prepares oil-soluble rare earth oxyfluoride nano material.The synthesis condition is easily controlled, reproducible, can obtain one
Serial rare-earth oxyfluoride, and the nano material prepared is in granular form, the dispersiveness of the particle, homogeneity and repeatability are equal
Very well.
Heretofore described " rare earth oxyfluoride " both include doping rare earth oxyfluoride, also include undoped with it is dilute
Native oxyfluoride.
By analyzing method of the prior art, it has been found that：In thermolysis process using single presoma, first,
Rare earth trifluoroacetate (i.e. a kind of rare earth trifluoroacetic acid complex) dissolves in a solvent, should when reaching certain reaction temperature
Rare earth trifluoroacetic acid complex decomposes generation rare earth-oxygen (Ln-O) key and fluorine ion (F-)；Secondly, in certain thermodynamic condition
Under, Ln-O keys can be with F-Rare earth oxyfluoride is generated, be i.e. fluorine oxidizing process, while rare earth fluoride can be generated again, that is, is fluorinated
Process.Because rare earth trifluoroacetic acid complex decomposes the F of generation-It is quantitatively more than Ln-O key, and F electronegativity is bigger than O, with
The coordination ability of rare earth ion is stronger, thus generally fluorination process account for it is leading, that is, be more easy to generate rare earth fluoride, cause
Fluoride dephasign content is high in product.The present invention is had found by studying, and second is added simultaneously in rare earth trifluoroacetate presoma
Sour ammonium can be very good as presoma when preparing oil-soluble rare earth oxyfluoride nano material using high-temperature solvent thermal decomposition method
Solve the above problems, its possible mechanism is：1) in specific solvent, the acetic acid root portion substitution trifluoroacetic acid root of ammonium acetate
Rare earth acetic acid complex is formed with rare-earth ion coordination；2) when reaching reaction temperature, rare earth trifluoroacetic acid complex decomposes life
Into rare earth-oxygen key (Ln-O keys), and discharge fluorine ion (F-)；Meanwhile rare earth acetic acid complex also decomposes generation Ln-O keys.
Under certain thermodynamic condition, Ln-O keys can be with F-Generate rare earth oxyfluoride, i.e. fluorine oxidizing process, while again can be with F-Generation
Rare earth fluoride, i.e. fluorination process.Due to rare earth acetic acid complex decompose generation Ln-O keys quantitatively with F-Quite, so as to
Suppress Ln-O keys and be fluorinated generation rare earth fluoride, efficiently control and avoid the fluoride dephasign in product.That is,
The ammonium acetate added, which has, provides oxonium ion, promotes the function of generation oxyfluoride so that synthesis side provided by the present invention
There is method synthesis condition to be easily controlled, it is reproducible the advantages that, and the nano material prepared is in granular form, and point of particle
It is fine to dissipate property, homogeneity and repeatability.
According to the present invention, the step of high-temperature solvent thermal decomposition method prepares oil-soluble rare earth oxyfluoride nano material, includes：
S1, rare earth trifluoroacetate and ammonium acetate being weighed at room temperature, solvent being added into the mixture of the two, it is molten to obtain solid mixing
Liquid；S2, solid mixed solution is heated and is incubated under inert gas shielding, such as 100~130 DEG C can be warming up to and be incubated
20~30 minutes, so that the reactant dissolving in solid mixed solution；S3, continue to heat under inert gas shielding and be incubated,
Such as be preferably heated to 280~330 DEG C and be incubated 1~2 hour, room temperature is cooled to, is centrifuged, is washed, is dried, it is molten to obtain oil
Property rare earth oxyfluoride nano material.
In the present invention, the nano material is in granular form, and the dispersiveness of the particle, homogeneity and repeatability are fine.
Specifically, the nano material is that oil-soluble rare earth oxyfluoride is nanocrystalline.
As the preferred embodiment of the present invention, the molar ratio of rare earth trifluoroacetate and ammonium acetate such as can be 1:(1
~1.5).When both mol ratios are located in above range, the more excellent rare earth oxyfluoride of performance can be obtained.Otherwise,
If mol ratio is too high easily rare earth oxide dephasign occurs, mol ratio is too low easily to there is rare earth fluoride dephasign.Therefore, pass through
Consider, the present invention preferably mol ratio of rare earth trifluoroacetate and ammonium acetate control is 1:(1~1.5).
According to the present invention, the solvent added into raw mixture for example can be the two of oleic acid, oleyl amine and octadecylene
Kind or three kinds of mixed solvent.As the presently preferred embodiments, in the mixed solvent oleic acid：Oleyl amine：The molar ratio of octadecylene such as can be with
It is 1:(1~2):(0~1).The present invention use above-mentioned mixed solvent mainly to consider to synthesize for rare earth oxyfluoride, and provide must
The factors such as the thermodynamic condition wanted.The mol ratio of above-mentioned three is defined in above-mentioned number range mainly in view of nanocrystalline
, otherwise easily there is the problems such as nanoparticle agglomerates in pattern governing factor.
According to the present invention, such as yttrium (Y), scandium can be contained in the product rare earth oxyfluoride nano material finally prepared
(Sc), 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) and one kind or any a variety of in lutetium (Lu).
According to the present invention, after obtaining oil-soluble rare earth oxyfluoride nano material, in addition to oil-soluble rare earth fluorine oxygen
Compound nano material carries out surface modification, to obtain the process of water miscible rare earth oxyfluoride nano material.Preferably, to oil
The step of rare earth oxyfluoride nano material progress surface modification of dissolubility, includes：Take the oil-soluble rare earth fluorine oxygen prepared in right amount
Compound nano material is scattered in chloro-carbon solvent (such as chloroform), is then added dropwise to the solution containing modifying agent
In, stir (such as stirring at normal temperature, mixing time are, for example, 12-36 hours, preferably 12 hours), stratification, take upper water to mix
Liquid is centrifuged, and the solid isolated is scrubbed, after drying, obtains water miscible rare earth oxyfluoride nano material.
Specifically, the modifying agent in the solution containing modifying agent is sodium citrate, and solution is ethanol and citric acid
Volume ratio (the mL of the mixture of sodium water solution (0.1~0.5mol/L, such as 0.2mol/L), ethanol and sodium citrate aqueous solution:
ML it is about) 1:1 (such as 2mL：2mL)；It is obtained be water miscible citric acid modification rare earth oxyfluoride it is nanocrystalline.
According to another aspect of the present invention, a kind of rare earth oxyfluoride nano material is additionally provided, it is to use above-mentioned
A kind of method is prepared.The rare earth oxyfluoride can be doping rare earth oxyfluoride or undoped with it is dilute
Native oxyfluoride.
The present invention a preferred embodiment in, the rare earth oxyfluoride nano material be it is rear-earth-doped or undoped with
MOF nano materials, M La, Gd or Y, it for example can be MOF:X%Eu is nanocrystalline, wherein, M La, Gd or Y, 0≤x≤
50, it is preferred that 0≤x≤10.Specific for example can be LaOF:5%Eu is nanocrystalline, GdOF:5%Eu is nanocrystalline, YOF:5%Eu
It is nanocrystalline.
The present invention another preferred embodiment in, the rare earth oxyfluoride nano material be it is rear-earth-doped or undoped with
Lu6O5F8Nano material, it for example can be Lu6O5F8:Y%Ln3+It is nanocrystalline, wherein, 0≤y≤50 (it is preferable, 0≤y≤
10), Ln3+One or more in Ce, Yb, Er, Tm, Ho, Eu, Gd, Tb, Dy, Sm, Nd and Pr.Such as can be
Lu6O5F8:Y%Eu3+It is nanocrystalline, 0≤y≤50 (preferable, 0≤y≤10)；Specific such as Lu6O5F8:5%Eu is nanocrystalline,
Lu6O5F8:40%Eu is nanocrystalline or Lu6O5F8It is nanocrystalline.Other for example can be Lu6O5F8:y1%Yb3+/y2%Er3+It is nanocrystalline,
0≤y1+y2≤ 50 (preferable, 0≤y1+y2≤ 30), for example, 10≤y1≤ 30,0≤y2≤10。
The present invention another preferred embodiment in, the rare earth oxyfluoride nano material be it is rear-earth-doped or undoped with
Eu6O5F8Nano material, it for example can be Eu6O5F8:Z%Ln3+It is nanocrystalline, 0≤z≤50 (preferable, 0≤z≤10),
Ln3+One or more in Ce, Yb, Er, Tm, Ho, Lu, Gd, Tb, Dy, Sm, Nd and Pr.Such as can be Eu6O5F8:
Z%Lu3+It is nanocrystalline, 0≤z≤50 (preferable, 0≤z≤10)；Specific such as Eu6O5F8:5%Lu is nanocrystalline, Eu6O5F8:40%Lu
Nanocrystalline or Eu6O5F8It is nanocrystalline.Other for example can be Eu6O5F8:z1%Yb3+/z2%Er3+It is nanocrystalline, 0≤z1+z2≤50
(preferable, 0≤z1+z2≤ 30), for example, 10≤z1≤ 30,0≤z2≤10。
Above-mentioned water miscible rare earth oxyfluoride nano material can be used for biological field, particularly for fluorescence mark
Remember biological detection and bio-imaging.It is preferred that the Lu of water-solubility rare-earth doping6O5F8Nano material can be in tumor-marker analyte detection
Using, or applied in medical imaging reagent is prepared.Figure 13 is middle rare earth doping Lu of the present invention6O5F8It is nanocrystalline to be examined in biology
Survey and the schematic diagram of imaging field application.
Specifically, in biological detection application, using Time-resolved fluorescence assay technology, Lu is realized6O5F8:Y%Eu3+Receive
Applications of the meter Jing (0≤y≤50) in tumor-marker analyte detection.In upper conversion imaging application, Lu6O5F8:Y%Yb3+/Er3+
Nanocrystalline (0≤y≤50) are excited by after cellular uptake using near infrared light (980nm), produce feux rouges and green glow, can be carried out thin
Born of the same parents are imaged.In CT imaging applications, Lu6O5F8It is nanocrystalline that there is higher CT values, CT contrast agent can be used as.It is further, water miscible
Lu6O5F8:Y%Yb/Er nanocrystalline (0≤y≤50) can apply in cell imaging or CT contrast agent.
Technical scheme is described in detail below by way of exemplary specific embodiment.But should not be by these
Embodiment is construed to limiting the scope of the invention.All technologies realized based on the above of the present invention are encompassed by this
Invention is intended in the range of protection.
Unless otherwise indicated, raw material and reagent described in embodiment are commercially available prod.
Instrument employed in the present invention is as follows：Testing nanocrystalline X-ray powder diffraction, (INSTRUMENT MODEL is
MiniFlex2, producer Rigaku, copper target radiation wavelength are λ=0.154187nm), transmission electron microscope (INSTRUMENT MODEL JEM-
2010, producer JEOL), nanocrystalline lower transfer excites, (INSTRUMENT MODEL FLS920, producer are launching light spectrogram
Edinburgh, excitation source are xenon lamp)
Embodiment 1
The oxidation of rare earth fluorine is prepared by the use of rare earth trifluoroacetate and ammonium acetate as the high-temperature solvent thermal decomposition method of presoma
Thing nano material：
(1) oil-soluble LaOF is prepared:5%Eu is nanocrystalline
0.5054g trifluoroacetic acids lanthanum, 0.0273g trifluoroacetic acids europium, 0.1156g ammonium acetates to three holes is weighed at room temperature to burn
Bottle, 5mL oleic acid, 9mL oleyl amines and 2mL octadecylenes are added as solvent.Be heated under an inert atmosphere above-mentioned trifluoroacetate and
310 DEG C are continuously heating to after ammonium acetate dissolving, reaction naturally cools to room temperature after 2 hours, precipitates and washs, obtains oil-soluble
LaOF:5%Eu is nanocrystalline.
From Fig. 1 a) in as can be seen that the oil solubility nanometer is brilliant to have a good crystallinity, its diffraction maximum position and relatively strong
Degree and LaOF PDF standard cards (JCPDS NO.77-0204) unanimously, belong to cubic system.
Such as Fig. 1 b) shown in, the oil solubility nanometer crystalline substance good dispersion, pattern are homogeneous, and particle diameter is about 3nm.
Such as Fig. 1 c) shown in, when it is 613nm to monitor wavelength, LaOF:PLE highest peak nanocrystalline 5%Eu is located at
At 273nm, belong to O2--Eu3+Charge migration transition, while occur Eu at 393nm3+Ion7F0-5L6Transition in 4f configurations.
As shown in Figure 1 d, under 268nm light source activations, LaOF:The nanocrystalline main peaks of launching of 5%Eu are located at the bright of 611nm
Azarin light, corresponding to Eu3+Ion5D0-7F2Electric dipole transition.
(2) oil-soluble GdOF is prepared:5%Eu is nanocrystalline
0.5228g trifluoroacetic acids gadolinium, 0.0273g trifluoroacetic acids europium, 0.1156g ammonium acetates to three holes is weighed at room temperature to burn
Bottle, 5mL oleic acid, 9mL oleyl amines are added as solvent；Above-mentioned trifluoroacetate and ammonium acetate are heated under an inert atmosphere to after dissolving
310 DEG C are continuously heating to, reaction naturally cools to room temperature after 2 hours, precipitates and washs, obtains oil-soluble GdOF:5%Eu nanometers
It is brilliant.
Such as Fig. 2 a) shown in, this is nanocrystalline to have good crystallinity, its diffraction maximum position and relative intensity and GdOF
PDF standard cards (JCPDS NO.50-0569) unanimously, belong to trigonal system.
Such as Fig. 2 b) shown in, nanocrystalline good dispersion, pattern are homogeneous, and particle diameter is about 4nm.
Such as Fig. 2 c) shown in, when it is 613nm to monitor wavelength, GdOF:PLE highest peak nanocrystalline 5%Eu is located at
At 270nm, belong to O2--Eu3+Charge migration transition；There is Gd in 273nm etc. simultaneously3+Ion8S7/2-6I7/2Jumped in 4f configurations
Move and occur Eu at 394nm3+Ion7F0-5L6Transition in 4f configurations.
Such as Fig. 2 d) shown in, under 268nm light source activations, GdOF:The nanocrystalline main peaks of launching of 5%Eu are located at the bright of 611nm
Azarin light, corresponding to Eu3+Ion5D0-7F2Electric dipole transition.
(3) oil-soluble YOF is prepared:5%Eu is nanocrystalline
0.4579g trifluoroacetic acids yttrium, 0.0273g trifluoroacetic acids europium, 0.0812g ammonium acetates to three holes is weighed at room temperature to burn
Bottle, 5mL oleic acid, 9mL oleyl amines are added as solvent；Above-mentioned trifluoroacetate and ammonium acetate are heated under an inert atmosphere to after dissolving
320 DEG C are continuously heating to, reaction naturally cools to room temperature after 2 hours, precipitates and washs, obtains oil-soluble YOF:5%Eu nanometers
It is brilliant.
Such as Fig. 3 a) shown in, it is nanocrystalline that there is good crystallinity, its diffraction maximum position and relative intensity and YOF PDF marks
Quasi- card (JCPDS NO.06-0347) unanimously, belongs to tetragonal crystal system.
Such as Fig. 3 b) shown in, nanocrystalline good dispersion, pattern are homogeneous, and particle diameter is about 5nm.
Such as Fig. 3 d) shown in, when it is 613nm to monitor wavelength, YOF:PLE highest peak nanocrystalline 5%Eu is located at
At 265nm, belong to O2--Eu3+Charge migration transition；Occurs Eu at 394nm simultaneously3+Ion7F0-5L6Transition in 4f configurations.
Such as Fig. 3 d) shown in, under 268nm light source activations, YOF:The nanocrystalline main peaks of launching of 5%Eu are located at the bright of 613nm
Azarin light, corresponding to Eu3+Ion5D0-7F2Electric dipole transition.
(4) oil-soluble Lu is prepared6O5F8:5%Eu is nanocrystalline
0.5397g trifluoroacetic acids lutetium, 0.0273g trifluoroacetic acids europium, 0.0812g ammonium acetates to three holes is weighed at room temperature to burn
Bottle, 5mL oleic acid, 9mL oleyl amines are added as solvent；After being heated to above-mentioned trifluoroacetate and ammonium acetate dissolving under an inert atmosphere
320 DEG C are continuously heating to, reaction naturally cools to room temperature after 2 hours, precipitates and washs, obtains oil-soluble Lu6O5F8:5%Eu receives
Meter Jing.
Such as Fig. 4 a) shown in, this is nanocrystalline to have good crystallinity, its diffraction maximum position and relative intensity and Wang Yuhua etc.
The Lu obtained by powder diffraction structure refinement6O5F8Consistent (the bibliography of standard diffraction spectrum：Wang Yuhua et al.,
Structure,enhancement and white luminescence of multifunctional Lu6O5F8:20%
Yb3+, 1%Er3+(Tm3+)nanoparticles via further doping with Li+under different
Excitation sources, Nanoscale, 5,2491-2504 (2013)), belong to rhombic system.
Such as Fig. 4 b) shown in, the nanocrystalline good dispersion, pattern are homogeneous, and particle diameter is about 5nm.
Such as Fig. 4 c) shown in, when it is 613nm to monitor wavelength, Lu6O5F8:PLE highest peak nanocrystalline 5%Eu is located at
At 394nm, belong to7F0-5L6Transition in 4f configurations；Occurs O at 262nm simultaneously2--Eu3+Charge migration transition.
Such as Fig. 4 d) shown in, under 393nm light source activations, Lu6O5F8:The nanocrystalline main peaks of launching of 5%Eu are located at 613nm's
Bright red, corresponding to Eu3+Ion5D0-7F2Electric dipole transition.
(5) oil-soluble Eu is prepared6O5F8It is nanocrystalline
0.5451g trifluoroacetic acids europium, 0.0812g ammonium acetates to three hole flasks are weighed at room temperature, add 5mL oleic acid, 9mL oil
Amine is as solvent；320 DEG C are continuously heating to after being heated to above-mentioned trifluoroacetate and ammonium acetate dissolving under an inert atmosphere, reaction
Room temperature is naturally cooled to after 2 hours, precipitates and washs, obtains oil-soluble Eu6O5F8It is nanocrystalline.
Such as Fig. 5 a) shown in, this is nanocrystalline to have good crystallinity, its diffraction maximum position and relative intensity and Eu6O5F8's
PDF standard cards (JCPDS NO.26-0637) unanimously, belong to rhombic system.
Such as Fig. 5 b) shown in, the nanocrystalline good dispersion, pattern are homogeneous, and particle diameter is about 5nm.
Such as Fig. 5 c) shown in, when it is 613nm to monitor wavelength, Eu6O5F8Nanocrystalline PLE highest peak is located at 393nm
Place, belongs to7F0-5L6Transition in 4f configurations；Occurs O at 274nm simultaneously2--Eu3+Charge migration transition.
Such as Fig. 5 d) shown in, under 393nm light source activations, Eu6O5F8:The nanocrystalline main peaks of launching of 5%Eu are located at 612nm's
Bright red, corresponding to Eu3+Ion5D0-7F2Electric dipole transition.
Embodiment 2
Based on dissolving Enhanced time resolved fluorometric immunoassay method, Lu is utilized6O5F8:Eu nano-probes carry out prostate
Specific antigen detects
1) oil-soluble Lu is prepared6O5F8:40%Eu is nanocrystalline
0.3408g trifluoroacetic acids lutetium, 0.2180g trifluoroacetic acids europium, 0.0812g ammonium acetates to three holes is weighed at room temperature to burn
Bottle, 5mL oleic acid, 9mL oleyl amines are added as solvent；After being heated to above-mentioned trifluoroacetate and ammonium acetate dissolving under an inert atmosphere
320 DEG C are continuously heating to, reaction naturally cools to room temperature after 2 hours, precipitates and washs, obtains oil-soluble Lu6O5F8:40%Eu
It is nanocrystalline.
Wherein, oil-soluble Lu6O5F8:Powder diagram and transmission electron microscope picture nanocrystalline 40%Eu is shown in Fig. 6 a) and figure
Shown in 6b).
2) water-soluble Lu is prepared6O5F8:40%Eu is nanocrystalline
The oil-soluble Lu prepared in 30mg steps 1) is weighed at room temperature6O5F8:40%Eu is nanocrystalline, is scattered in the chloromethanes of 2mL tri-
In alkane, the in the mixed solvent of 2mL ethanol/2mL sodium citrate aqueous solutions (0.2mol/L), and stirring at normal temperature are then added dropwise to
12 hours.Finally, by mixed solution stratification, draw upper strata aqueous phase solution and centrifuged in centrifuge tube, that isolates consolidates
Body is scrubbed, after drying, obtains the water-soluble Lu of the i.e. citric acid modification of solid product6O5F8:40%Eu is nanocrystalline.
3) water miscible Lu6O5F8:The nanocrystalline coupling Avidins (avidin) of 40%Eu
Water-solubility nanocrystalline obtained by 1mg steps 2) is scattered in 1mL 10mmol/L 2- (N- morpholines) ethyl sulfonic acid (MES)
In buffer solution, and with 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDC) (20mmol/L) and N- hydroxyls
Succinimide (NHS) (50mmol/L) activates 3 hours at room temperature.Then, the nanocrystalline of activation is centrifuged, washed
Wash, and be added to 1mL dissolved with Avidin (1mg/mL) phosphate buffer (PBS), vibrate and be incubated 12 hours at 4 DEG C.
Finally it is centrifuged nanocrystalline, wash, producing coupling has the water-solubility nanocrystalline of Avidin.
4) enhancing liquid is prepared
Weigh 1g Triton X-100,26.6mg naphthoyltrifluoroacetone (β-NTA), 193mg trioctylphosphines
(TOPO), add distilled water and be settled to 1L, pH value is adjusted to 2.76 with glacial acetic acid.
5)Lu6O5F8:The nanocrystalline double-antibody method detection PSAs of 40%Eu
(a) it is coated with：The antibody of PSA is diluted to 10 μ g/ with 0.1mol/L carbonate buffer solution
ML, in 96 hole polystyrene plates, 100 μ L are added per hole, 37 DEG C are incubated 1 hour, liquid in hole are discarded, with PBST washing buffers
Liquid is washed 3 times.
(b) close：0.1% monoethanolamine is prepared with 0.1mol/L carbonate buffer solution, adds 300 μ L per hole, 37 DEG C
It is incubated 1 hour, removes liquid in hole, washed 3 times with PBST lavation buffer solutions.
(c) it is loaded：0-50ng/mL PSA series standard solution is prepared with PBS, makes its dense
Degree is respectively：0ng/mL、0.0008ng/mL、0.0025ng/mL、0.0076ng/mL、0.0229ng/mL、0.0686ng/mL、
0.2058ng/mL, 0.6173ng/mL, 1.8519ng/mL, 5.5556ng/mL, 16.6667ng/mL, 50ng/mL standard items,
37 DEG C are incubated 1 hour, discard liquid in hole, are washed 3 times with PBST lavation buffer solutions.
(d) biotinylated antibody is added：2 μ g/mL biotinylated antibody is prepared with PBS, 100 μ are added per hole
L, 37 DEG C are incubated 1 hour, discard liquid in hole, are washed 3 times with PBST lavation buffer solutions.
(e) Lu of coupling Avidin is added6O5F8:40%Eu is nanocrystalline：20 μ g/mL step 3) institute is prepared with PBS
The water-soluble Lu of the coupling Avidin obtained6O5F8:40%Eu is nanocrystalline, 100 μ L is added per hole, 37 DEG C are incubated 1 hour, discard hole
Interior liquid, washed 6 times with PBST lavation buffer solutions.
(f) enhancing liquid is added：200 μ l enhancing liquid is added per hole, fluorescence signal is detected using time resolution, design parameter is：
Excitation wavelength 340nm, launch wavelength 614nm, the μ s of time delay 200.
(g) standard curve is drawn：Using PSA concentration of standard solution as abscissa, with each concentration
Fluorescence intensity corresponding to standard liquid is ordinate, draws standard curve, as shown in Figure 7.In 0.0008-5.5556ng/mL models
In enclosing, the concentration of PSA is linear related to fluorescence intensity, y=962.1x+263.8, R2=0.9975.With
Blank averages add 3 times of standard deviations to estimate that lowest detection is limited to 0.5pg/mL.
(h) measure of sample：100 μ l testing samples are added in step (c), other steps are same as above, by testing sample
Fluorescence intensity brings calibration curve equation into, tries to achieve corresponding concentration value.
Embodiment 3
Lu6O5F8:Application performance detection nanocrystalline Yb/Er
(1) oil-soluble Lu is prepared6O5F8:20%Yb/2%Er is nanocrystalline
Weigh at room temperature 0.4431g trifluoroacetic acids lutetium, 0.1132g trifluoroacetic acids ytterbium, 0.0112 trifluoroacetic acid erbium,
0.0812g ammonium acetates add 5mL oleic acid, 9mL oleyl amines as solvent to three hole flasks；Above-mentioned three are heated under an inert atmosphere
320 DEG C are continuously heating to after fluoroacetate and ammonium acetate dissolving, reaction naturally cools to room temperature after 2 hours, precipitates and washs, obtains
To oil-soluble Lu6O5F8:20%Yb/2%Er is nanocrystalline.
Fig. 8 a) and 8b) be Lu6O5F8:Powder diagram and transmission electron microscope picture nanocrystalline 20%Yb/2%Er.
As shown in figure 9, in the case where 980nm near infrared lights excite, typical green glow (520-570nm) and feux rouges is presented in the material
(640-670nm) Up-conversion emission, is corresponded respectively to2H11/2/4S3/2Arrive4I15/2, and4F9/2Arrive4I15/2Transition.
(2) water-soluble Lu is prepared6O5F8:20%Yb/2%Er is nanocrystalline
The oil-soluble Lu obtained in 30mg steps (1) is weighed at room temperature6O5F8:20%Yb/2%Er is nanocrystalline to be scattered in 2mL
In chloroform, the in the mixed solvent of 2ml ethanol/2mL sodium citrate aqueous solutions (0.2mol/L) is then added dropwise to, and often
Temperature stirring 12 hours.Finally, by mixed solution stratification, draw upper strata aqueous phase solution and centrifuged in centrifuge tube, separated
The solid that goes out is scrubbed, dry after, obtain the water-solubility nanocrystalline of the i.e. manufactured citric acid modification of solid product.
(3) biological safety is tested：As shown in Figure 10, prepared water-soluble Lu6O5F8:20%Yb/2%Er is nanocrystalline,
Under the conditions of non-illumination and illumination 2 minutes, in 0~1mg/mL concentration ranges, with normal human embryonic lung fibroblasts (HELF)
It is incubated 12 hours, HELF cell survival rates illustrate the water-soluble Lu more than 95%6O5F8:The nanocrystalline tools of 20%Yb/2%Er
There is biological safety.
(4) transition cell imaging effect is tested on：As shown in figure 11, prepared water-soluble Lu6O5F8:20%Yb/2%
Er is nanocrystalline to can be applied to cell imaging.Concentration is 0.5mg/mL water-soluble Lu6O5F8:20%Yb/2%Er it is nanocrystalline with
Human lung carcinoma cell (H1299) is washed after being incubated 2 hours in 37 DEG C with PBS, closely red with 980nm under confocal fluorescent microscope
Outer light excites, and green emission (520~560nm) and red emission (640~680nm) in cell can be observed.
(5) CT imaging effects are tested：As shown in figure 12, water-soluble Lu6O5F8:20%Yb/2%Er is nanocrystalline, 3.125
In~25mg/mL concentration ranges, as concentration increases, CT signal enhancings.CT values are 319HU when concentration is 12.5mg/mL, and same
The Iopromide CT values of concentration commercialization only have 186HU, illustrate that the nano material is expected to turn into new class CT contrast agent.
Claims (15)
1. a kind of preparation method of rare earth oxyfluoride nano material, it uses rare earth trifluoroacetate and ammonium acetate as forerunner
Body, and high-temperature solvent thermal decomposition method is utilized, so as to obtain oil-soluble rare earth oxyfluoride nano material.
2. preparation method according to claim 1, it is characterised in that prepared using high-temperature solvent thermal decomposition method oil-soluble
The step of rare earth oxyfluoride nano material, includes：
S1, rare earth trifluoroacetate and ammonium acetate are weighed at room temperature, solvent is added into the mixture of the two, obtain solid and mix
Close solution；
S2, the solid mixed solution is heated and is incubated under inert gas shielding, so that the reaction in solid mixed solution
Thing dissolves；
S3, continue to heat under inert gas shielding and be incubated, be cooled to room temperature, centrifuge, wash, dry, obtain described
Oil-soluble rare earth oxyfluoride nano material.
3. preparation method according to claim 2, it is characterised in that by the solid mixed solution in the step S2
It is heated to 100~130 DEG C and is incubated 20~30 minutes, so that the reactant dissolving in solid mixed solution.
4. preparation method according to claim 2, it is characterised in that 280~330 DEG C are heated in the step S3 simultaneously
Insulation 1~2 hour.
5. according to the preparation method described in claim any one of 1-4, it is characterised in that the rare earth trifluoroacetate and described
The mol ratio of ammonium acetate is 1:(1~1.5).
6. preparation method according to claim 2, it is characterised in that the solvent is the two of oleic acid, oleyl amine and octadecylene
Kind or three kinds of mixed solvent.
7. preparation method according to claim 6, it is characterised in that in the mixed solvent oleic acid, oleyl amine and the octadecylene
Mol ratio be 1:(1~2):(0~1).
8. according to the preparation method described in claim any one of 1-4, it is characterised in that the rare earth trifluoroacetate be selected from Y,
One or more in Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu trifluoroacetate.
9. according to the preparation method described in claim any one of 1-4, it is characterised in that also include to the oil-soluble rare earth
Oxyfluoride nano material carries out surface modification, to obtain the process of water miscible rare earth oxyfluoride nano material.
10. preparation method according to claim 9, it is characterised in that to the oil-soluble rare earth oxyfluoride nanometer
The step of material progress surface modification, includes：
Take the appropriate oil-soluble rare earth oxyfluoride nano material to be scattered in chloro-carbon solvent, be then added dropwise to
In solution containing modifying agent, stirring, stratification, upper strata aqueous phase solution is taken to be centrifuged, the solid isolated is scrubbed, dry
After dry, water miscible rare earth oxyfluoride nano material is obtained.
11. preparation method according to claim 10, it is characterised in that the chloro-carbon solvent is chloroform.
12. preparation method according to claim 10, it is characterised in that the stirring is stirring at normal temperature, and mixing time is
12-36 hours.
13. preparation method according to claim 10, it is characterised in that the modifying agent in the solution containing modifying agent
For sodium citrate, solution is the mixture of ethanol and sodium citrate aqueous solution, ethanol and sodium citrate aqueous solution in terms of mL
Volume ratio is 1:1；It is obtained be water miscible citric acid modification rare earth oxyfluoride it is nanocrystalline.
14. preparation method according to claim 13, it is characterised in that the concentration of the sodium citrate aqueous solution is 0.1
~0.5mol/L.
15. preparation method according to claim 14, it is characterised in that the concentration of the sodium citrate aqueous solution is
0.2mol/L。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510903999.5A CN105505392B (en) | 2015-12-09 | 2015-12-09 | Rare earth oxyfluoride nano material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510903999.5A CN105505392B (en) | 2015-12-09 | 2015-12-09 | Rare earth oxyfluoride nano material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105505392A CN105505392A (en) | 2016-04-20 |
| CN105505392B true CN105505392B (en) | 2018-02-02 |
Family
ID=55713702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510903999.5A Active CN105505392B (en) | 2015-12-09 | 2015-12-09 | Rare earth oxyfluoride nano material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105505392B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106340592A (en) * | 2016-10-09 | 2017-01-18 | 南昌航空大学 | Preparation of rare earth colloid quantum dot and application in quantum dot solar battery |
| JP6388188B1 (en) * | 2016-11-02 | 2018-09-12 | 日本イットリウム株式会社 | Film forming material and film |
| CN108102652B (en) * | 2016-11-24 | 2019-09-20 | 中国科学院福建物质结构研究所 | A kind of rare earth Oxybromide nano material and its preparation method and application |
| KR101979082B1 (en) * | 2017-05-10 | 2019-05-16 | 신라대학교 산학협력단 | Upconversion Phosphors Comprising Non Stoichiometric Host and Method of Manufacturing Same |
| JP7147675B2 (en) * | 2018-05-18 | 2022-10-05 | 信越化学工業株式会社 | Thermal spray material and method for producing thermal spray member |
| CN111607295A (en) * | 2020-03-11 | 2020-09-01 | 浙江纳美新材料股份有限公司 | Waterborne fluorescent color paste for invisible anti-counterfeiting two-dimensional code and preparation method thereof |
| CN113304313A (en) * | 2020-12-29 | 2021-08-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of injectable calcium phosphate bone cement modified by drug-loaded rare earth MOF, and product and application thereof |
| CN116023944A (en) * | 2021-10-26 | 2023-04-28 | 中国科学院福建物质结构研究所 | H (H) + Ion doped luminescent-enhanced rare earth inorganic nano luminescent material, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3767588A (en) * | 1971-01-29 | 1973-10-23 | Hitachi Ltd | Infrared excitable rare earth oxyfluoride luminescent materials |
| CN101209898A (en) * | 2006-12-27 | 2008-07-02 | 中国科学院福建物质结构研究所 | Erbium-doped barium-yttrium-fluoride-nanocrystalline containing transparent oxyfluoride glass ceramic and preparation thereof |
-
2015
- 2015-12-09 CN CN201510903999.5A patent/CN105505392B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3767588A (en) * | 1971-01-29 | 1973-10-23 | Hitachi Ltd | Infrared excitable rare earth oxyfluoride luminescent materials |
| CN101209898A (en) * | 2006-12-27 | 2008-07-02 | 中国科学院福建物质结构研究所 | Erbium-doped barium-yttrium-fluoride-nanocrystalline containing transparent oxyfluoride glass ceramic and preparation thereof |
Non-Patent Citations (4)
| Title |
|---|
| "Band structure, shape controllable synthesis and luminescence properties of the precursor and final product Lu6O5F8:Eu/Tb/Ce/Dy nano/microstructures";L. Guo et al.，;《J. Mater. Chem. C》;20131017;第1卷(第47期);第7952-7962页 * |
| "Distinct structural and optical correlations of Y1-xEuxOF and Yn(1-x)EunxOn-1Fn+2 (x=0.001–0.1, n=6, 7)vernier phosphors";S. Park et al.，;《Journal ofLuminescence》;20150529;第166卷;第176-179页 * |
| "Structure, enhancement and white luminescence of multifunctional Lu6O5F8:20%Yb3+,1%Er3+(Tm3+) nanoparticles via further doping with Li+ under different excitation sources";L. Guo et al.，;《Nanoscale》;20130103;第5卷(第6期);第2491-2504页 * |
| "Synthesis, spectroscopic and structural studies on YOF, LaOF and GdOF nanocrystals doped with Eu3+, synthesized via stearic acid method";T. Grzyb et al.，;《Optical Materials》;20130629;第35卷(第12期);第2226-2233页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105505392A (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105505392B (en) | Rare earth oxyfluoride nano material and its preparation method and application | |
| Liu et al. | Controlled synthesis and optical spectroscopy of lanthanide-doped KLaF 4 nanocrystals | |
| Goldys et al. | Optical characterization of Eu-doped and undoped Gd2O3 nanoparticles synthesized by the hydrogen flame pyrolysis method | |
| Chen et al. | Ultrasmall monodisperse NaYF4: Yb3+/Tm3+ nanocrystals with enhanced near-infrared to near-infrared upconversion photoluminescence | |
| Cao et al. | Hydrothermal synthesis and enhanced photoluminescence of Tb 3+ in Ce 3+/Tb 3+ doped KGdF 4 nanocrystals | |
| Song et al. | Gd 2 O 2 S: Yb, Er submicrospheres with multicolor upconversion fluorescence | |
| CN107033905A (en) | A kind of rear-earth-doped lithium yttrium fluoride nano material and preparation method and application | |
| Huang et al. | Tunable upconversion of holmium sublattice through interfacial energy transfer for anti-counterfeiting | |
| Liu et al. | Microwave synthesis and luminescent properties of YVO4: Ln3+ (Ln= Eu, Dy and Sm) phosphors with different morphologies | |
| CN103224787B (en) | Rear-earth-doped alkali earth metal fluoride nano material and its preparation and application | |
| CN102703081B (en) | Water-soluble rare earth doped gadolinium sodium tetrafluoride fluorescent marked nano-crystal, and preparation method thereof | |
| Mahata et al. | Photon-upconverting materials: advances and prospects for various emerging applications | |
| CN107722967B (en) | A method of red fluorescence emits in enhancing ytterbium/holmium/cerium codope fluorine lutetium natrium nanocrystalline body | |
| Chen et al. | Size-dependent downconversion near-infrared emission of NaYF 4: Yb 3+, Er 3+ nanoparticles | |
| CN113817469B (en) | Ultra-bright monochromatic up-conversion nano probe for excitation/emission in biological window and preparation method and application thereof | |
| Jain et al. | Rare-earth-doped Y3Al5O12 (YAG) nanophosphors: synthesis, surface functionalization, and applications in thermoluminescence dosimetry and nanomedicine | |
| Chen et al. | Dual mode emission of core–shell rare earth nanoparticles for fluorescence encoding | |
| Liu et al. | Carbon dot-based nanocomposite: Long-lived thermally activated delayed fluorescence for lifetime thermal sensing | |
| CN107163937A (en) | A kind of rear-earth-doped zirconium fluoride lithium nano luminescent material with loose structure and its preparation method and application | |
| Chen et al. | Synthesis and Luminescence Properties of Water Soluble α-NaGdF 4/β-NaYF 4: Yb, Er Core–Shell Nanoparticles | |
| Zheng et al. | Upconversion luminescence and temperature sensing properties of NaGd (WO 4) 2: Yb 3+/Er 3+@ SiO 2 core–shell nanoparticles | |
| Wei et al. | Recent progress in synthesis of lanthanide-based persistent luminescence nanoparticles | |
| CN102504820B (en) | Preparation method of up-conversion fluorescence/paramagnetic difunctional nanocrystal | |
| Wang et al. | Lanthanide-doped LaOBr nanocrystals: controlled synthesis, optical spectroscopy and bioimaging | |
| Li et al. | A latest-generation fluoride with excellent structural stiffness for ultra-efficient photoluminescence and specific four-peak emission temperature sensing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |