CN110452682A - A kind of method that one kettle way is prepared on a large scale rare-earth doping fluoride nano crystalline substance - Google Patents
A kind of method that one kettle way is prepared on a large scale rare-earth doping fluoride nano crystalline substance Download PDFInfo
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Abstract
The present invention provides a kind of methods that one kettle way is prepared on a large scale rare-earth doping fluoride nano crystalline substance；It specifically provides a kind of one kettle way and is prepared on a large scale rear-earth-doped AREF4Nanocrystalline and AREF4@A’RE’F4The method of nano-crystal with core-shell structure, this method have universality, directly utilize AHF2Powder is as the source F and alkali metal source, it does not need using trifluoroacetate and methanol, time needed for improving the safety of reaction and shortening reaction, synthesized nanocrystalline even size distribution, luminescent properties are excellent, especially after coating shell, obtained core-shell nano trichite light enhances decades of times.The low in raw material price that this method uses, it is reaction process safety, simple, time-consuming short, it can amplify that synthesis particle is uniform, rear-earth-doped AREF of Qiang Faguang4Nanocrystalline and AREF4@A’RE’F4Core-shell nano is brilliant, has paved road for the rear-earth-doped practical large-scale application of inorganic nano-crystal material.
Description
Technical field
The invention belongs to nanometer synthesis technical fields, and in particular to a kind of one kettle way is prepared on a large scale rare-earth-doped fluoride
Nanocrystalline method.
Background technique
Rare earth ion has electronic energy level structure abundant, and the transition between energy level is more, thus can emit from it is ultraviolet to
The light of infrared various wave bands.In recent years, rear-earth-doped inorganic nano material is controlled in super-resolution imaging, biological living imaging, disease
Treat etc. all embodies great application value.Luminescent properties are best, most widely used in rare-earth doping fluoride nano crystalline substance
A kind of compound such as AREF4, wherein A is alkali metal element, and RE is rare earth element；Due to its with high upper conversion/lower turn
It moves luminous efficiency and excellent physical and chemical stability and receives widest concern.AREF4Pass through codope Yb3+,Er3+
(or Tm3+,Ho3+) etc. Up-conversion emission from ultraviolet light near infrared light may be implemented, pass through codope Ce3+,Tb3+Or Yb3+,
Er3+Emit etc. visible light may be implemented to the lower transfer of near infrared light.In addition, also using rare earth luminescence fluorescence lifetime
The features such as long and near-infrared excites, may be implemented the biological detection or imaging of no background, therefore rear-earth-doped AREF4In
The fields such as biological fluorescent labelling application show tempting actual application prospect.
Various sizes of rear-earth-doped AREF4Nanocrystalline optics and other physicochemical properties difference are very big, but big
Batch synthesizes uniform AREF4Nanocrystalline (being greater than 10g) is still a greatly challenge.As bioprobe in the neck such as detection
The application in domain needs repeatability and reliability well, it is therefore desirable to develop that a kind of to be prepared on a large scale out appearance and size equal
One, the preparation method of good dispersion.
At present document mainly utilize high temperature thermal decomposition method (document J.Am.Chem.Soc.2006,128,6426-6436) and
High temperature coprecipitation (document Nat.Protoc.2014,9,1634-1644) laboratory scale prepares on a small quantity rear-earth-doped
AREF4Nanocrystalline (≤1g), but since the influence factor of synthesis is numerous, thus the often rear-earth-doped AREF of every one-pot synthesis4It receives
Meter Jing has different sizes and pattern.And using high temperature thermal decomposition method and high temperature coprecipitation be prepared on a large scale it is rear-earth-doped
AREF4Nanocrystalline process can encounter many problems.For example rear-earth-doped AREF is prepared on a large scale using high temperature thermal decomposition method4It receives
When rice is brilliant, since used presoma is trifluoroacetate, and when heating reaction, these trifluoroacetates can acutely divide
Solution, generates a large amount of toxic gases.In addition, these gases can generate a large amount of foams in organic solvent, so that organic solvent
It ejects, thus reacts than relatively hazardous, be not suitable for being prepared on a large scale rear-earth-doped AREF4It is nanocrystalline.Relative to high warm point
For solution, the reaction of high temperature coprecipitation is milder, however Fluorine source used in high temperature coprecipitation and sodium source needs are first molten
Solution usually synthesizes the rear-earth-doped AREF of 1mmol into methanol4It is nanocrystalline to need 10mL methanol, therefore needed when high-volume synthesizes
Very big reaction vessel is wanted, additionally due to methanol boiling point is relatively low, in order to avoid bumping, therefore is discharged anti-set by methanol
Answering temperature is usually 50 degrees centigrades, so the time discharge methanol for needing to grow very much in high temperature coprecipitation.In addition, by
It is affected in the toxicity of methanol to the nervous system and hematological system of human body, methanol steam is through alimentary canal, respiratory tract or skin
Take in energy loss victimize respiratory mucosa and eyesight, therefore also limit high temperature coprecipitation be prepared on a large scale it is rear-earth-doped
AREF4Nanocrystalline application.In conclusion being badly in need of developing a kind of safe operation, simplicity, time saving, economic and can be controllably at present
It is prepared on a large scale rear-earth-doped AREF4Nanocrystalline preparation method.
Summary of the invention
In order to improve the deficiencies in the prior art, the object of the present invention is to provide a kind of one kettle way be prepared on a large scale it is rear-earth-doped
Fluoride nano crystal, such as AREF4Nanocrystalline and AREF4@A’RE’F4The method of nano-crystal with core-shell structure, the method can be significantly
The dosage demand for reducing raw material, can not only disposably synthesize large batch of AREF4It is nanocrystalline, it can be with large batch of acquisition ruler
The uniform AREF of very little distribution4@A’RE’F4Nano-crystal with core-shell structure, a yield are up to tens gram quantity grades.The present invention is with AHF2
Powder is as Fluorine source and alkali metal source, and cheap, reaction process is mild, safety, simple process, time-consuming short, organic solvent
Usage amount can decline 85% with respect to conventional method, obtained nano-crystalline granule uniform particle diameter, with excellent luminescent properties, can
To be advantageously applied to the fields such as biological detection and imaging, this method is suitble to industrial-scale preparation, for rear-earth-doped nothing in the future
The nanocrystalline large-scale application of machine is laid a good foundation.
The present invention is achieved through the following technical solutions:
It is a kind of to prepare rear-earth-doped AREF4Nanocrystalline method, which comprises by least one rare earth precursor,
Oleic acid, octadecylene and AHF2Mixing, heating obtain the rear-earth-doped AREF4It is nanocrystalline, wherein A is alkali metal element, is selected from
Lithium (Li), sodium (Na), potassium (K), rubidium (Rb) or caesium (Cs)；RE is rare earth element, is selected from yttrium (Y), scandium (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) or one of lutetium (Lu) or any a variety of.
Preferably, it is warming up to 160-360 DEG C.It is further preferred that being warming up to 160-360 DEG C keeps the temperature 0.1~3 hour.
Preferably, the reaction carries out under an inert atmosphere.
According to the present invention, which comprises at least one rare earth precursor, oleic acid and octadecylene are mixed and heated up molten
Solution, is added AHF after cooling2, heating obtains the rear-earth-doped AREF again4It is nanocrystalline.
Preferably, at least one rare earth precursor, oleic acid and octadecylene mix and are warming up to 60-230 DEG C.It is further preferred that
At least one rare earth precursor, oleic acid and octadecylene mix and are warming up to 60-230 DEG C and keep the temperature 0.1~3 hour.
Preferably, AHF is added2Afterwards, it is warming up to 160-360 DEG C again.It is further preferred that AHF is added2Afterwards, it is warming up to again
160-360 DEG C and heat preservation 0.1~3 hour.
According to the present invention, it the described method comprises the following steps:
(1) at least one rare earth precursor, oleic acid and octadecylene are mixed, under inert gas protection rising temperature for dissolving,
Then it is down to room temperature, obtains mixed solution；
(2) AHF is added into the mixed solution of step (1)2Heat up and insulation reaction for a period of time；
(3) continue to heat up and keep the temperature a period of time on the basis of step (2), then cool down, obtain described rear-earth-doped
AREF4It is nanocrystalline.
According to the present invention, the rare earth precursor is selected from lanthanon acetate, one of rare earth-iron-boron or any a variety of.
According to the present invention, the rare earth in the rare earth precursor is selected from yttrium (Y), scandium (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) or
One of lutetium (Lu) is any a variety of.
According to the present invention, the total volume of the corresponding oleic acid of every 1mmol rare earth precursor and octadecylene is 3mL~30mL；It is excellent
It is selected as 15mL~25mL.
Preferably, the volume ratio of the oleic acid and octadecylene is 0.1~10.
According to the present invention, it in step (1), is warming up to 60-230 DEG C and keeps the temperature 0.1~3 hour.
According to the present invention, the AHF2Molar ratio with rare earth precursor is 1~4.
According to the present invention, it in step (2), is warming up to 160-330 DEG C and keeps the temperature 0.1~3 hour, be preferably warming up to 160-
280 DEG C and heat preservation 0.1~3 hour.
Preferably, the reaction carries out under the protection of the inert gases such as such as nitrogen, helium.
According to the present invention, it in step (3), is continuously heating to 280-360 DEG C and keeps the temperature 0.1~3 hour, preferably continue to heat up
To 290-360 DEG C and keep the temperature 0.1~3 hour.
Rear-earth-doped AREF is prepared the present invention also provides a kind of4@A’RE’F4The method of nano-crystal with core-shell structure, the method
The rear-earth-doped AREF is prepared including above-mentioned4Nanocrystalline method.
According to the present invention, the method also includes following steps:
To rear-earth-doped AREF4At least one rare earth precursor and A ' as shell presoma is added in nanocrystalline system
HF2, heat up and obtain the rear-earth-doped AREF4@A’RE’F4Nano-crystal with core-shell structure；
The AREF4As nuclear structure, the A ' RE ' F4As shell structure；And the A and A ' are identical or different, each other solely
On the spot selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) or caesium (Cs)；RE and RE ' are identical or different, are independently from each other yttrium
(Y), scandium (Sc), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium
(Ho), one of erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu) or any a variety of.
Preferably, it is warming up to 160-360 DEG C.It is further preferred that being warming up to 160-360 DEG C keeps the temperature 0.1~3 hour.
Preferably, the reaction carries out under an inert atmosphere.
According to the present invention, the method also includes following steps:
To rear-earth-doped AREF4At least one rare earth precursor and liter as shell presoma is added in nanocrystalline system
Temperature dissolution, is added AHF after cooling2, heating obtains the rear-earth-doped AREF again4@A’RE’F4Nano-crystal with core-shell structure.
Preferably, rear-earth-doped AREF4At least one rare earth forerunner as shell presoma is added in nanocrystalline system
Body is simultaneously warming up to 60-230 DEG C.It is further preferred that rear-earth-doped AREF4It is added in nanocrystalline system at least one as shell forerunner
The rare earth precursor of body is simultaneously warming up to 60-230 DEG C and keeps the temperature 0.1~3 hour.
Preferably, A ' HF is added2Afterwards, it is warming up to 160-360 DEG C again.It is further preferred that A ' HF is added2Afterwards, it is warming up to again
160-360 DEG C and heat preservation 0.1~3 hour.
According to the present invention, the method also includes following steps:
(4) to rear-earth-doped AREF4At least one rare earth precursor as shell presoma is added in nanocrystalline system,
Then rising temperature for dissolving under inert gas protection is down to room temperature, obtain mixed solution；
(5) A ' HF is added into the mixed solution of step (4)2Heat up and insulation reaction for a period of time；
(6) continue to heat up and keep the temperature a period of time on the basis of step (5), then cool down, obtain described rear-earth-doped
AREF4@A’RE’F4Nano-crystal with core-shell structure.
According to the present invention, the rare earth in the rare earth precursor as shell presoma is selected from yttrium (Y), scandium (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), one of ytterbium (Yb) or lutetium (Lu) or any a variety of.
According to the present invention, the rare earth precursor as shell presoma and rear-earth-doped AREF is prepared4Nanocrystalline
The molar ratio of rare earth precursor is 0.1~3.
According to the present invention, it in step (4), is warming up to 60-230 DEG C and keeps the temperature 0.1~3 hour.
According to the present invention, the A ' HF2Molar ratio with the rare earth precursor as shell presoma is 1~4.
According to the present invention, it in step (5), is warming up to 160-330 DEG C and keeps the temperature 0.1~3 hour；It is preferred that being warming up to 160-
280 DEG C and heat preservation 0.1~3 hour.
Preferably, the reaction carries out under the protection of the inert gases such as such as nitrogen, helium.
According to the present invention, it in step (6), is continuously heating to 280-360 DEG C and keeps the temperature 0.1~3 hour, preferably continue to heat up
To 290-360 DEG C and keep the temperature 0.1~3 hour.
The utility model has the advantages that
The present invention provides a kind of methods that one kettle way is prepared on a large scale rare-earth doping fluoride nano crystalline substance；It specifically provides
A kind of one kettle way is prepared on a large scale rear-earth-doped AREF4Nanocrystalline and AREF4@A’RE’F4The method of nano-crystal with core-shell structure,
This method has universality, can easily amplify and synthesize a series of AREF4Nanocrystalline and AREF4@A’RE’F4Nucleocapsid knot
Structure is nanocrystalline, such as NaSmF4、NaEuF4、NaGdF4、NaTbF4、NaYF4、NaEuF4@NaEuF4、NaGdF4@NaGdF4、NaGdF4@
NaYF4、NaYF4@NaGdF4、NaYF4@NaYF4Deng.In addition, the present invention directly utilizes AHF2Powder as the source F and alkali metal source,
When this method is not needed needed for being substantially increased the safety of reaction using trifluoroacetate and methanol and shortening reaction
Between, it is very suitable to be prepared on a large scale AREF4Nanocrystalline and AREF4@A’RE’F4Nano-crystal with core-shell structure, synthesized is nanocrystalline
Even size distribution, luminescent properties are excellent, and especially after coating shell, obtained core-shell nano trichite light enhances number
Ten times.Method of the invention can decline 85% relative to traditional usage amount by optimization solvent strength, the usage amount of solvent.We
The low in raw material price that method uses, reaction process safety, simple, time-consuming is short, and it is uniform, Qiang Faguang dilute can to amplify synthesis particle
Soil doping AREF4Nanocrystalline and AREF4@A’RE’F4Core-shell nano is brilliant, for the practical big rule of rear-earth-doped inorganic nano-crystal material
Road has been paved in mould application.
Detailed description of the invention
Fig. 1 is the NaGdF of embodiment 14: Yb, Er nanocrystalline X-ray powder diffraction figure.
Fig. 2 is the NaGdF of embodiment 14: Yb, Er nanocrystalline transmission electron microscope picture.
Fig. 3 is the NaEuF of embodiment 24Nanocrystalline X-ray powder diffraction figure.
Fig. 4 is the NaEuF of embodiment 24Nanocrystalline transmission electron microscope picture.
Fig. 5 is the NaGdF of embodiment 34:Yb,Er@NaYF4The X-ray powder diffraction figure of nano-crystal with core-shell structure.
Fig. 6 is the NaGdF of embodiment 34:Yb,Er@NaYF4The transmission electron microscope picture of nano-crystal with core-shell structure.
Fig. 7 is the NaGdF of embodiment 34:Yb,Er@NaYF4Before and after the cladding of nano-crystal with core-shell structure under 980nm excitation
Up-conversion emission spectra.
Fig. 8 is the NaYF of embodiment 44:Yb,Er@NaYF4The transmission electron microscope picture of nano-crystal with core-shell structure.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Instrument and equipment:
In the present invention, the test equipment model MiniFlex2 of the X-ray powder diffraction figure, producer Rigaku, copper
Target emanation wavelength is λ=0.154187nm.
In the present invention, test equipment the model JSM-6700F, producer JEOL of the transmission electron microscope picture.
In the present invention, the test equipment model FLS980 type (Edinburgh of the up-conversion emission spectra
Instrument), excitation light source is 980nm semiconductor laser.
Embodiment 1:200mmol NaGdF4: Yb, Er nanocrystalline preparation
160mmol gadolinium acetate, 36mmol acetic acid ytterbium and 4mmol acetic acid erbium are weighed, and 400mL oleic acid, 200mL 18 is added
Alkene is warming up to 180 DEG C under nitrogen protection and stirs 30 minutes, is cooled to room temperature and 400mmol NaHF is added2Powder, in nitrogen
It is warming up to 250 DEG C under protection and stirs 30 minutes, then raise temperature to 310 DEG C and stirs 30 minutes, last cooled to room temperature,
Centrifugation, washing obtain 200mmolNaGdF4: Yb, Er are nanocrystalline.
Fig. 1 is NaGdF4: Yb, Er nanocrystalline X-ray powder diffraction figure shows that the product of synthesis is hexagonal phase NaGdF4:
Yb,Er；
Fig. 2 is NaGdF4: Yb, Er nanocrystalline transmission electron microscope picture, it can be seen that its partial size is 23.5nm.
Moreover, it will be understood by those skilled in the art that passing through the type and concentration of Doped ions in feed change, In
In the case that other synthesis conditions are constant, the NaGdF of different Doped ions or different levels of doping can be prepared4Nanocrystalline
Sample, and by once-through operation, the sample of 200mmol can be obtained.
Embodiment 2:200mmol NaEuF4Nanocrystalline preparation
200mmol acetic acid europium is weighed, and 400mL oleic acid, 200mL octadecylene is added, is warming up to 180 DEG C under nitrogen protection
And stir 30 minutes, it is cooled to room temperature and 400mmol NaHF is added2Powder is warming up to 250 DEG C under nitrogen protection and stirs 30
Minute, it then raises temperature to 310 DEG C and stirs 30 minutes, last cooled to room temperature, centrifugation, washing obtain 200mmol
NaEuF4It is nanocrystalline.
Fig. 3 is NaEuF4Nanocrystalline X-ray powder diffraction figure shows that the product of synthesis is hexagonal phase NaEuF4；
Fig. 4 is NaEuF4Nanocrystalline transmission electron microscope picture, it can be seen that its partial size is 9.6nm.
Embodiment 3:200mmol NaGdF4:Yb,Er@NaYF4The preparation of nano-crystal with core-shell structure
160mmol gadolinium acetate, 36mmol acetic acid ytterbium and 4mmol acetic acid erbium are weighed, and 400mL oleic acid, 200mL 18 is added
Alkene is warming up to 180 DEG C under nitrogen protection and stirs 30 minutes, is cooled to room temperature and 400mmol NaHF is added2Powder, in nitrogen
It is warming up to 250 DEG C under protection and stirs 30 minutes, then raise temperature to 310 DEG C and stirs 30 minutes, cooled to room temperature, then
100mmol acetic acid yttrium is added, be warming up to 180 DEG C under nitrogen protection and stirs 30 minutes, is cooled to room temperature and 200mmol is added
NaHF2Powder is warming up to 250 DEG C under nitrogen protection and stirs 30 minutes, then raises temperature to 310 DEG C and stirring 30 minutes, most
Cooled to room temperature afterwards, centrifugation, washing obtain 200mmol NaGdF4:Yb,Er@NaYF4Nano-crystal with core-shell structure.
Fig. 5 is NaGdF4:Yb,Er@NaYF4The X-ray powder diffraction figure of nano-crystal with core-shell structure shows the product of synthesis
It is pure hexagonal phase NaGdF4:Yb,Er@NaYF4；
Fig. 6 is NaGdF4:Yb,Er@NaYF4The transmission electron microscope picture of nano-crystal with core-shell structure, it can be seen that its partial size is
27.8nm, wherein the illustration in Electronic Speculum is NaGdF4:Yb,Er@NaYF4Nanocrystalline weighing, weight 63.38g；
Fig. 7 is the nanocrystalline up-conversion luminescence comparison under 980nm excitation in cladding front and back, and up-conversion luminescence enhances after cladding
17 times.
Embodiment 4:200mmol NaYF4:Yb,Er@NaYF4The preparation of nano-crystal with core-shell structure
160mmol acetic acid yttrium, 36mmol acetic acid ytterbium and 4mmol acetic acid erbium are weighed, and 400mL oleic acid, 200mL 18 is added
Alkene is warming up to 180 DEG C under nitrogen protection and stirs 30 minutes, is cooled to room temperature and 400mmol NaHF is added2Powder, in nitrogen
It is warming up to 250 DEG C under protection and stirs 30 minutes, then raise temperature to 310 DEG C and stirs 30 minutes, cooled to room temperature, then
100mmol acetic acid yttrium is added, be warming up to 180 DEG C under nitrogen protection and stirs 30 minutes, is cooled to room temperature and 200mmol is added
NaHF2Powder is warming up to 250 DEG C under nitrogen protection and stirs 30 minutes, then raises temperature to 310 DEG C and stirring 30 minutes, most
Cooled to room temperature afterwards is centrifuged, washs, being dried to obtain 200mmol NaYF4:Yb,Er@NaYF4Nano-crystal with core-shell structure.
Fig. 8 is NaYF4:Yb,Er@NaYF4The transmission electron microscope picture of nano-crystal with core-shell structure, it can be seen that its partial size is
110nm。
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of prepare rear-earth-doped AREF4Nanocrystalline method, which is characterized in that the described method includes: by least one rare earth
Presoma, oleic acid, octadecylene and AHF2Mixing, heating obtain the rear-earth-doped AREF4It is nanocrystalline, wherein A is alkali metal member
Element, selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) or caesium (Cs)；RE is rare earth element, is selected from yttrium (Y), scandium (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), one of ytterbium (Yb) or lutetium (Lu) or any a variety of.
2. the method according to claim 1, wherein being warming up to 160-360 DEG C.
Preferably, it is warming up to 160-360 DEG C and keeps the temperature 0.1~3 hour.
Preferably, the reaction carries out under an inert atmosphere.
3. method according to claim 1 or 2, which is characterized in that the described method includes: by least one rare earth forerunner
Body, oleic acid and octadecylene mixing and rising temperature for dissolving, are added AHF after cooling2, heating obtains the rear-earth-doped AREF again4It receives
Meter Jing.
Preferably, at least one rare earth precursor, oleic acid and octadecylene mix and are warming up to 60-230 DEG C.
Preferably, at least one rare earth precursor, oleic acid and octadecylene mix and are warming up to 60-230 DEG C and keep the temperature 0.1~3 small
When.
Preferably, AHF is added2Afterwards, it is warming up to 160-360 DEG C again.
Preferably, AHF is added2Afterwards, it is warming up to 160-360 DEG C again and keeps the temperature 0.1~3 hour.
4. method according to claim 1-3, which is characterized in that the described method comprises the following steps:
(1) at least one rare earth precursor, oleic acid and octadecylene are mixed, under inert gas protection rising temperature for dissolving, then
It is down to room temperature, obtains mixed solution；
(2) AHF is added into the mixed solution of step (1)2Heat up and insulation reaction for a period of time；
(3) continue to heat up and keep the temperature a period of time on the basis of step (2), then cool down, obtain the rear-earth-doped AREF4
It is nanocrystalline.
5. method according to claim 1-4, which is characterized in that the rare earth precursor is selected from rare earth acetic acid
Salt, one of rare earth-iron-boron or any a variety of.
Preferably, the total volume of the corresponding oleic acid of every 1mmol rare earth precursor and octadecylene is 3mL~30mL；Preferably 15mL
~25mL.
Preferably, the volume ratio of the oleic acid and octadecylene is 0.1~10.
Preferably, it in step (1), is warming up to 60-230 DEG C and keeps the temperature 0.1~3 hour.
Preferably, the AHF2Molar ratio with rare earth precursor is 1~4.
Preferably, it in step (2), is warming up to 160-330 DEG C and keeps the temperature 0.1~3 hour, be preferably warming up to 160-280 DEG C and protect
Temperature 0.1~3 hour.
Preferably, the reaction carries out under the protection of the inert gases such as such as nitrogen, helium.
Preferably, it in step (3), is continuously heating to 280-360 DEG C and keeps the temperature 0.1~3 hour, preferably continue to be warming up to 290-
360 DEG C and heat preservation 0.1~3 hour.
6. a kind of prepare rear-earth-doped AREF4@A’RE’F4The method of nano-crystal with core-shell structure, the method includes claim 1-
5 described in any item rear-earth-doped AREF4Nanocrystalline method.
Preferably, the method also includes following steps:
To rear-earth-doped AREF4At least one rare earth precursor as shell presoma and A ' HF are added in nanocrystalline system2,
Heating obtains the rear-earth-doped AREF4@A’RE’F4Nano-crystal with core-shell structure；
The AREF4As nuclear structure, the A ' RE ' F4As shell structure；And the A and A ' are identical or different, independently of one another
Selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) or caesium (Cs)；RE and RE ' are identical or different, be independently from each other yttrium (Y),
Scandium (Sc), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho),
One of erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu) are any a variety of.
7. according to the method described in claim 6, it is characterized in that, being warming up to 160-360 DEG C.
Preferably, it is warming up to 160-360 DEG C and keeps the temperature 0.1~3 hour.
Preferably, the reaction carries out under an inert atmosphere.
8. method according to claim 6 or 7, which is characterized in that the method also includes following steps:
To rear-earth-doped AREF4At least one rare earth precursor as shell presoma is added in nanocrystalline system and is heated up molten
Solution, is added AHF after cooling2, heating obtains the rear-earth-doped AREF again4@A’RE’F4Nano-crystal with core-shell structure.
Preferably, rear-earth-doped AREF4At least one rare earth precursor and liter as shell presoma is added in nanocrystalline system
Temperature is to 60-230 DEG C.It is further preferred that rear-earth-doped AREF4It is added in nanocrystalline system at least one as the dilute of shell presoma
Native presoma is simultaneously warming up to 60-230 DEG C and keeps the temperature 0.1~3 hour.
Preferably, A ' HF is added2Afterwards, it is warming up to 160-360 DEG C again.It is further preferred that A ' HF is added2Afterwards, it is warming up to 160- again
360 DEG C and heat preservation 0.1~3 hour.
9. according to the described in any item methods of claim 6-8, which is characterized in that the method also includes following steps:
(4) to rear-earth-doped AREF4At least one rare earth precursor as shell presoma is added in nanocrystalline system, lazy
Rising temperature for dissolving under property gas shield, is then down to room temperature, obtains mixed solution；
(5) A ' HF is added into the mixed solution of step (4)2Heat up and insulation reaction for a period of time；
(6) continue to heat up and keep the temperature a period of time on the basis of step (5), then cool down, obtain the rear-earth-doped AREF4@
A’RE’F4Nano-crystal with core-shell structure.
10. the method according to claim 6, which is characterized in that before the rare earth as shell presoma
It drives body and prepares rear-earth-doped AREF4The molar ratio of nanocrystalline rare earth precursor is 0.1~3.
Preferably, it in step (4), is warming up to 60-230 DEG C and keeps the temperature 0.1~3 hour.
Preferably, the A ' HF2Molar ratio with the rare earth precursor as shell presoma is 1~4.
Preferably, it in step (5), is warming up to 160-330 DEG C and keeps the temperature 0.1~3 hour；It is preferred that being warming up to 160-280 DEG C and protecting
Temperature 0.1~3 hour.
Preferably, the reaction carries out under the protection of the inert gases such as such as nitrogen, helium.
Preferably, it in step (6), is continuously heating to 280-360 DEG C and keeps the temperature 0.1~3 hour, preferably continue to be warming up to 290-
360 DEG C and heat preservation 0.1~3 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111171820A (en) * | 2019-12-23 | 2020-05-19 | 华南师范大学 | Etching method of rare earth fluoride up-conversion nanocrystal |
| CN112625687A (en) * | 2021-01-28 | 2021-04-09 | 福州大学 | Rare earth doped elpasolite nanometer luminescent material and preparation method thereof |
| CN113125400A (en) * | 2021-04-20 | 2021-07-16 | 中国计量大学上虞高等研究院有限公司 | Luminescent nanocrystalline material and preparation method and application thereof |
| CN113969071A (en) * | 2020-10-23 | 2022-01-25 | 深圳优易材料科技有限公司 | High-temperature anti-sticking coating capable of catalytically decomposing dioxin |
| CN116333741A (en) * | 2023-04-07 | 2023-06-27 | 福州大学 | Rare earth doped sulfur oxide/fluoride heterogeneous core-shell structure nano luminescent material |
Citations (1)
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| CN104388087A (en) * | 2014-11-21 | 2015-03-04 | 武汉理工大学 | Method for preparing rare-earth fluorescent up-conversion material by use of waste fluorescent powder |
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| CN104927863B (en) * | 2015-06-05 | 2017-06-13 | 武汉理工大学 | The nanocrystalline method of hexagonal phase sodium yttrium tetrafluoride that rare earth metal is co-doped with is prepared using waste phosphor powder |
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| CN104388087A (en) * | 2014-11-21 | 2015-03-04 | 武汉理工大学 | Method for preparing rare-earth fluorescent up-conversion material by use of waste fluorescent powder |
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| CN111171820A (en) * | 2019-12-23 | 2020-05-19 | 华南师范大学 | Etching method of rare earth fluoride up-conversion nanocrystal |
| CN111171820B (en) * | 2019-12-23 | 2021-12-21 | 华南师范大学 | Etching method of rare earth fluoride up-conversion nanocrystal |
| CN113969071A (en) * | 2020-10-23 | 2022-01-25 | 深圳优易材料科技有限公司 | High-temperature anti-sticking coating capable of catalytically decomposing dioxin |
| CN112625687A (en) * | 2021-01-28 | 2021-04-09 | 福州大学 | Rare earth doped elpasolite nanometer luminescent material and preparation method thereof |
| CN113125400A (en) * | 2021-04-20 | 2021-07-16 | 中国计量大学上虞高等研究院有限公司 | Luminescent nanocrystalline material and preparation method and application thereof |
| CN113125400B (en) * | 2021-04-20 | 2022-10-18 | 中国计量大学上虞高等研究院有限公司 | Luminescent nanocrystalline material and preparation method and application thereof |
| CN116333741A (en) * | 2023-04-07 | 2023-06-27 | 福州大学 | Rare earth doped sulfur oxide/fluoride heterogeneous core-shell structure nano luminescent material |
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