CN108676560A - A kind of fluoride nano crystal composite material and preparation method - Google Patents
A kind of fluoride nano crystal composite material and preparation method Download PDFInfo
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- CN108676560A CN108676560A CN201810350539.8A CN201810350539A CN108676560A CN 108676560 A CN108676560 A CN 108676560A CN 201810350539 A CN201810350539 A CN 201810350539A CN 108676560 A CN108676560 A CN 108676560A
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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- 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
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Abstract
The invention belongs to field of inorganic materials, it is related to a kind of nanocrystalline composite material and preparation method thereof.A kind of fluoride nano crystal composite material, the composite material is by hexagonal phase NaGdF4Nanocrystalline and tetragonal phase Na3ZrF7Nanocrystalline two kinds of presomas are obtained using surface chemistry bonding action.The present invention proposes a kind of nanocrystalline composite material for being prepared by bond to surface and having different crystal structure, and the flexible modulation of excitation wavelength and launch wavelength may be implemented, and realizes the multicolor luminous of multiband excitation.Second object of the present invention is to provide the preparation method of above-mentioned composite material, and this method is at low cost, yield is high, and products therefrom good dispersion, combined efficiency are high.
Description
Technical field
The invention belongs to field of inorganic materials, it is related to a kind of nanocrystalline composite material and preparation method thereof.
Background technology
In recent years, conversion nano crystalline substance is square in bio-imaging, biological detection, biomarker etc. on rare earth ion doped fluoride
Face has potential application and is concerned.Rare earth ion energy level is very abundant, can be real in different basis materials
The existing different characteristics of luminescence, such as controllable transmitting of the erbium ion from green light to feux rouges may be implemented by crystal structure regulation and control, this
It is advantageously implemented multicolor luminous.And nanocrystalline composite material is built, the flexible modulation of excitation wavelength and launch wavelength may be implemented,
I.e. multiband excitation is multicolor luminous.
Invention content
It is an object of the present invention to provide a kind of fluoride nano crystal composite material, which uses
NaGdF4Nanocrystalline and Na3HfF7The flexible modulation of excitation wavelength and launch wavelength may be implemented in nanocomposite, realizes more waves
Duan Jifa's is multicolor luminous.Second object of the present invention is to provide the preparation method of above-mentioned composite material, this method cost
It is low, yield is high, products therefrom good dispersion, combined efficiency are high.
In order to realize first above-mentioned purpose, present invention employs technical solutions below：
A kind of fluoride nano crystal composite material, the composite material is by hexagonal phase NaGdF4Nanocrystalline and tetragonal phase Na3HfF7Nanometer
Brilliant two kinds of presomas are obtained using surface chemistry bonding action.
Preferably, the hexagonal phase NaGdF4Nanocrystalline and tetragonal phase Na3HfF7Nanocrystalline molar ratio is 3:1-1:
1。
In order to realize second above-mentioned purpose, present invention employs technical solutions below：
A method of the fluoride nano crystal composite material being prepared, this approach includes the following steps：
1）Prepare the NaGdF that carboxyl is contained on surface4It is nanocrystalline；
2）Prepare the Na that amino is contained on surface3HfF7It is nanocrystalline；
3）Gained NaGdF4Nanocrystalline and Na3HfF7It is nanocrystalline with 3:1-1:1 molar ratio mixes in deionized water, in room
Temperature lower stirring 24-48 hours, freeze-dried acquisition fluoride nano crystal composite material.
Preferably, the step 1）Include the following steps：
1）By 10-20% mole of acetic acid gadoliniums, 8-12 milliliters of oleic acid are added in three-neck flask, under the protective condition of inert gas,
After keeping the temperature 0.5 ~ 2 hour at a temperature of 150 ~ 170 DEG C, 12-16 milliliters of octadecylenes are added into three-neck flask, 150 ~ 170
After keeping the temperature 0.5 ~ 2 hour at a temperature of DEG C, clear solution A is obtained；
2）After solution A naturally cools to room temperature, contain 30-60% moles of ammonium fluoride and 10-30% moles of hydroxide by 5 ~ 7 milliliters
The methanol solution of sodium is added dropwise in solution A, then keeps the temperature 0.4 ~ 1 hour at 75 ~ 85 DEG C；
3）Wait for that methanol solution all after volatilization, is brought rapidly up 280-300 DEG C, and keep the temperature 90-120 minutes at this temperature,
Then room temperature is naturally cooled to；It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by NaGdF4Nanocrystalline guarantor
There are spare in hexamethylene；
4）By gained NaGdF4Nanocrystal solution is added to containing hydrochloric acid：Citric acid=1:5-1:In 20 mixed liquor, through ultrasound
24-48 hours, obtain the NaGdF that carboxyl is contained on surface4It is nanocrystalline.
Preferably, the inert gas is one kind in nitrogen, neon, argon gas.
Preferably, the step 2）Include the following steps：
1）By 10-20% moles of acetylacetone,2,4-pentanedione zirconium, 20-40% mole of acetic acid is received, and 6-8 milliliters of oleic acid are added in three-neck flask,
Under the protective condition of inert gas, after keeping the temperature 0.5 ~ 2 hour at a temperature of 140 ~ 160 DEG C, 8-12 is added into three-neck flask
Milliliter octadecylene, continues heat preservation 0.5 ~ 2 hour at a temperature of 150 ~ 160 DEG C, obtains clear solution B；
2）After B solution naturally cools to room temperature, 8 milliliters of methanol solutions containing 20-60% moles of ammonium fluoride are added dropwise to
In B solution, then 0.4 ~ 1 hour is kept the temperature at 75 ~ 85 DEG C；
3）Wait for that methanol solution all after volatilization, is brought rapidly up 250-270 DEG C, and keep the temperature 30-90 minutes at this temperature, so
After naturally cool to room temperature；It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by Na3HfF7Nanocrystalline preservation
It is spare in hexamethylene；
4）By the Na of gained3HfF7Nanocrystal solution is added to containing hydrochloric acid：Polyethyleneimine=1:5-1:In 20 mixed liquor,
Through 48-72 hours ultrasonic, the Na of amino is contained on acquisition surface3HfF7It is nanocrystalline.
Preferably, the inert gas is one kind in nitrogen, neon, argon gas.
The fluoride nano crystal composite material of the present invention, the composite material is by hexagonal phase NaLnF4Nanocrystalline and tetragonal phase
Na3HfF7Nanocrystalline or Na3ZrF7Nanocrystalline two kinds of presomas are obtained using surface chemistry bonding action；The Ln=Y, La,
Gd or Lu.
As a further improvement, hexagonal phase NaLnF4It is nanocrystalline to use rare earth doped, described rare earth member
Element is to include selected from one or more of Eu, Tb, Sm, Dy, Yb, Nd, Pr, Er, Ho, Tm, Ce.It is only needed in preparation method
Gadolinium is adulterated using respective element.
As a further improvement, tetragonal phase Na3HfF7Nanocrystalline, Na3ZrF7It is nanocrystalline also to be mixed using rare earth element
Miscellaneous, the rare earth element is to include selected from one or more of Eu, Tb, Sm, Dy, Yb, Nd, Pr, Er, Ho, Tm, Ce.
It only needs to adulterate Hf using respective element in preparation method.
A method of fluoride nano crystal composite material being prepared, this approach includes the following steps：
1）Prepare the NaLnF that carboxyl is contained on surface4It is nanocrystalline；
2）Prepare the Na that amino is contained on surface3HfF7Nanocrystalline or Na3ZrF7It is nanocrystalline；
3）Gained NaLnF4Nanocrystalline and Na3HfF7Nanocrystalline or Na3ZrF7It is nanocrystalline with 3:1-1:3 molar ratio go from
It mixes, is stirred at room temperature 24-48 hours in sub- water, freeze-dried acquisition fluoride nano crystal composite material.
The present invention proposes a kind of nanocrystalline composite material for being prepared by bond to surface and having different crystal structure, and
The method that routine prepares nanocrystalline composite material is obtained by epitaxial growth method, and this method is suitable only for lattice constant and crystalline substance
System similar in body structure.It is characterized in that, first to nanocrystalline carry out selective surface's modification of different crystal structure,
A kind of middle surface functional group of the surface cladding with carboxyl, another then surface functional group of the cladding with amino utilize amino
Bonding action between carboxyl obtains nanocrystalline composite material.This method provides to prepare fluoride nano crystal composite material
A kind of completely new thinking is conducive to the further development in nano material synthesis field.
The present invention's additionally provides a kind of anti-counterfeiting ink, and the aqueous solution of the fluoride nano crystal composite material is added
Or do not add ink conventional material as fluorescent ink be directly used in printing and it is hand-written.Print or it is hand-written go out image in purple
It is visible under outer lamp.
The present invention's additionally provides a kind of biomarker, uses above-mentioned fluoride nano crystal composite material.
Above-mentioned fluoride nano crystal composite material can also be applied to isolating and purifying for cell and biomolecule.
Preparation method of the present invention is at low cost, yield is high, and products therefrom good dispersion, combined efficiency are high, and suitable preparation has
The nanocrystalline composite material of property.The preparation method of this novel fluoride nano crystal composite material is expected in nanometer material
Material synthesis field is widely used.
Description of the drawings
NaGdF in Fig. 1, embodiment 14Nanocrystalline X-ray diffractogram.
NaGdF in Fig. 2, embodiment 14Nanocrystalline transmission electron microscope picture.
NaGdF in Fig. 3, embodiment 14Nanocrystalline energy spectrum diagram.
Na in Fig. 4, embodiment 13HfF7Nanocrystalline X-ray diffractogram.
Na in Fig. 5, embodiment 13HfF7Nanocrystalline transmission electron microscope picture.
Na in Fig. 6, embodiment 13HfF7Nanocrystalline energy spectrum diagram.
NaGdF in Fig. 7, embodiment 14- Na3HfF7The transmission electron microscope picture of nanocrystalline composite material.
Ce/Tb in Fig. 8, embodiment 2:NaGdF4Nanocrystalline X-ray diffractogram.
Yb/Ho in Fig. 9, embodiment 2:Na3ZrF7Nanocrystalline X-ray diffractogram.
Ce/Tb in Figure 10, embodiment 2:NaGdF4- Yb/Ho:Na3ZrF7The X-ray diffractogram of nanocrystalline composite material.
Specific implementation mode
Embodiment 1:
1. by 1 mM of gadolinium, 8 milliliters of oleic acid are added in three-neck flask, under the protective condition of nitrogen, at 160 DEG C
At a temperature of keep the temperature 1 hour after, into three-neck flask be added 12 milliliters of octadecylenes, continue at a temperature of 160 DEG C heat preservation 1 hour,
Obtain clear solution A.After solution A naturally cools to room temperature, contain 3 mMs of ammonium fluorides and 1.5 mMs of hydrogen-oxygens by 6 milliliters
The methanol solution for changing sodium is added dropwise in solution A, then keeps the temperature half an hour at 80 DEG C.After waiting for that methanol solution all volatilizees,
It is brought rapidly up to 280 DEG C, and keeps the temperature 90 minutes at this temperature, then naturally cool to room temperature.Ethyl alcohol is used by gained is nanocrystalline
It is washed with hexamethylene mixed liquor, finally by NaGdF4It is nanocrystalline be stored in it is spare in 4ml hexamethylenes.
2. being added to gained nanocrystal solution in 1 containing hydrochloric acid：Citric acid=1:It is small through ultrasound 48 in 10 mixed liquor
When, obtain the NaGdF that carboxyl is contained on surface4It is nanocrystalline.
3. by 0.5 mM of acetylacetone,2,4-pentanedione hafnium, 1.5 mMs of acetic acid are received, and 6 milliliters of oleic acid are added in three-neck flask,
Under the protective condition of nitrogen, after keeping the temperature 1 hour at a temperature of 150 DEG C, 8 milliliters of octadecylenes are added into three-neck flask, 155
Continue heat preservation 1 hour at a temperature of DEG C, obtains clear solution B.After B solution naturally cools to room temperature, contain 2 millis by 8 milliliters
The methanol solution of mole ammonium fluoride is added dropwise in B solution, then keeps the temperature half an hour at 80 DEG C.Wait for that methanol solution all volatilizees
Later, it is brought rapidly up to 270 DEG C, and keeps the temperature 60 minutes at this temperature, then naturally cool to room temperature.By the nanocrystalline use of gained
Ethyl alcohol and the washing of hexamethylene mixed liquor, finally by Na3HfF7It is nanocrystalline be stored in it is spare in 4ml hexamethylenes.
4. being added to gained nanocrystal solution in 3 containing hydrochloric acid：Polyethyleneimine=1:In 5 mixed liquor, through ultrasound
72 hours, obtain the Na that amino is contained on surface3HfF7It is nanocrystalline.
5. gained in 2 and 4 is nanocrystalline with 2:1 ratio mixes in 10 ml deionized waters, is stirred at room temperature 48
Hour, freeze-dried acquisition fluoride nano crystal composite material.
Powder x-ray diffraction analysis：Synthesized precursor product is respectively hexagonal phase NaGdF4It is nanocrystalline（Fig. 1）With four
Square phase Na3HfF7It is nanocrystalline（Fig. 2）, NaGdF4Nanocrystalline average grain size is 6nm（Fig. 3）, Na3HfF7Nanocrystalline is averaged
Crystallite dimension is 65nm（Fig. 4）, EDAX results show NaGdF4Contain Na, Gd and F element in nanocrystalline（Fig. 5）,
Na3HfF7Contain Na, Hf and F element in nanocrystalline（Fig. 6）.Fig. 7 shows that two kinds of presomas constitute nanometer through bond to surface
Crystal composite material.
Embodiment 2:
1. by 0.75 mM of gadolinium, 0.2 mM of cerous acetate, 0.05 mole of acetic acid terbium, 8 milliliters of oleic acid are added to three necks burning
In bottle, under the protective condition of nitrogen, 160oAfter keeping the temperature 1 hour at a temperature of C, 12 milliliter 18 is added into three-neck flask
Alkene, 160oContinue heat preservation 1 hour at a temperature of C, obtains clear solution A.After solution A naturally cools to room temperature, by 6 milliliters
Methanol solution containing 3 mMs of ammonium fluorides and 1.5 mMs of sodium hydroxides is added dropwise in solution A, then 80oC is protected
Warm half an hour.Wait for that methanol solution all after volatilization, is brought rapidly up to 280oC, and 90 minutes are kept the temperature at this temperature, then certainly
So it is cooled to room temperature.It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by Ce/Tb:NaGdF4Nanocrystalline guarantor
There are spare in 4ml hexamethylenes.
2. being added to gained nanocrystal solution in 1 containing hydrochloric acid：Citric acid=1:It is small through ultrasound 48 in 10 mixed liquor
When, obtain the Ce/Tb that carboxyl is contained on surface:NaGdF4It is nanocrystalline.
3. by 0.39 mM of acetylacetone,2,4-pentanedione zirconium, 0.1 mM of ytterbium acetate, 0.01 mM of acetic acid holmium, 1.5 mMs of second
Sour sodium, 6 milliliters of oleic acid are added in three-neck flask, under the protective condition of nitrogen, 150oAfter 1 hour being kept the temperature at a temperature of C,
8 milliliters of octadecylenes are added into three-neck flask, 155oContinue heat preservation 1 hour at a temperature of C, obtains clear solution B.Wait for that B is molten
After liquid naturally cools to room temperature, 8 milliliters of methanol solutions containing 2 mMs of ammonium fluorides are added dropwise in B solution, are then existed
80oC keeps the temperature half an hour.Wait for that methanol solution all after volatilization, is brought rapidly up to 270oC, and 60 minutes are kept the temperature at this temperature,
Then room temperature is naturally cooled to.It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by Yb/Ho:Na3HfF7It receives
Meter Jing is stored in spare in 4ml hexamethylenes.
4. being added to gained nanocrystal solution in 3 containing hydrochloric acid：Polyethyleneimine=1:In 5 mixed liquor, through ultrasound
72 hours, obtain the Yb/Ho that amino is contained on surface:Na3ZrF7It is nanocrystalline.
5. gained in 2 and 4 is nanocrystalline with 2:1 ratio mixes in 10 ml deionized waters, is stirred at room temperature 48
Hour, freeze-dried acquisition fluoride nano crystal composite material.
Powder x-ray diffraction analysis：Synthesized precursor product is respectively hexagonal phase NaGdF4It is nanocrystalline（Fig. 8）With four
Square phase Na3ZrF7It is nanocrystalline（Fig. 9）.Figure 10 shows that two kinds of presomas constitute nanocrystalline composite material through bond to surface.
Ce/Tb:NaGdF4- Yb/Ho:Na3ZrF7Nanocrystalline composite material can generate bright under the ultraviolet lamp shooting condition of 254nm wavelength
Bright green emission.Ce/Tb:NaGdF4- Yb/Ho:Na3ZrF7Nanocrystalline composite material is excited in the laser of 980nm wavelength
Under the conditions of can generate bright yellow emission.
Embodiment 3
1. by 0.75 mM of gadolinium, 0.2 mM of cerous acetate, 0.05 mole of acetic acid europium, 8 milliliters of oleic acid are added to three necks burning
In bottle, under the protective condition of nitrogen, 160oAfter keeping the temperature 1 hour at a temperature of C, 12 milliliter 18 is added into three-neck flask
Alkene, 160oContinue heat preservation 1 hour at a temperature of C, obtains clear solution A.After solution A naturally cools to room temperature, by 6 milliliters
Methanol solution containing 3 mMs of ammonium fluorides and 1.5 mMs of sodium hydroxides is added dropwise in solution A, then 80oC is protected
Warm half an hour.Wait for that methanol solution all after volatilization, is brought rapidly up to 280oC, and 90 minutes are kept the temperature at this temperature, then certainly
So it is cooled to room temperature.It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by Ce/Eu:NaGdF4Nanocrystalline guarantor
There are spare in 4ml hexamethylenes.
2. being added to gained nanocrystal solution in 1 containing hydrochloric acid：Citric acid=1:It is small through ultrasound 48 in 10 mixed liquor
When, obtain the Ce/Eu that carboxyl is contained on surface:NaGdF4It is nanocrystalline.
3. by 0.39 mM of acetylacetone,2,4-pentanedione zirconium, 0.1 mM of ytterbium acetate, 0.01 mM of acetic acid holmium, 1.5 mMs of second
Sour sodium, 6 milliliters of oleic acid are added in three-neck flask, under the protective condition of nitrogen, 150oAfter 1 hour being kept the temperature at a temperature of C,
8 milliliters of octadecylenes are added into three-neck flask, 155oContinue heat preservation 1 hour at a temperature of C, obtains clear solution B.Wait for that B is molten
After liquid naturally cools to room temperature, 8 milliliters of methanol solutions containing 2 mMs of ammonium fluorides are added dropwise in B solution, are then existed
80oC keeps the temperature half an hour.Wait for that methanol solution all after volatilization, is brought rapidly up to 270oC, and 60 minutes are kept the temperature at this temperature,
Then room temperature is naturally cooled to.It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by Yb/Ho:Na3HfF7It receives
Meter Jing is stored in spare in 4ml hexamethylenes.
4. being added to gained nanocrystal solution in 3 containing hydrochloric acid：Polyethyleneimine=1:In 5 mixed liquor, through ultrasound
72 hours, obtain the Yb/Ho that amino is contained on surface:Na3ZrF7It is nanocrystalline.
5. gained in 2 and 4 is nanocrystalline with 2:1 ratio mixes in 10 ml deionized waters, is stirred at room temperature 48
Hour, freeze-dried acquisition fluoride nano crystal composite material.
Ce/Eu:NaGdF4- Yb/Ho:Na3ZrF7Nanocrystalline composite material energy under the conditions of the burst of ultraviolel of 254nm wavelength
Generate bright red emission.
Embodiment 4:
1. by 0.75 mM of acetic acid lutetium, 0.2 mM of cerous acetate, 0.05 mole of acetic acid terbium, 8 milliliters of oleic acid are added to three necks burning
In bottle, under the protective condition of nitrogen, 160oAfter keeping the temperature 1 hour at a temperature of C, 12 milliliter 18 is added into three-neck flask
Alkene, 160oContinue heat preservation 1 hour at a temperature of C, obtains clear solution A.After solution A naturally cools to room temperature, by 6 milliliters
Methanol solution containing 3 mMs of ammonium fluorides and 1.5 mMs of sodium hydroxides is added dropwise in solution A, then 80oC is protected
Warm half an hour.Wait for that methanol solution all after volatilization, is brought rapidly up to 280oC, and 90 minutes are kept the temperature at this temperature, then certainly
So it is cooled to room temperature.It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by Ce/Tb:NaLuF4Nanocrystalline guarantor
There are spare in 4ml hexamethylenes.
2. being added to gained nanocrystal solution in 1 containing hydrochloric acid：Citric acid=1:It is small through ultrasound 48 in 10 mixed liquor
When, obtain the Ce/Tb that carboxyl is contained on surface:NaLuF4It is nanocrystalline.
3. by 0.39 mM of acetylacetone,2,4-pentanedione zirconium, 0.1 mM of ytterbium acetate, 0.01 mM of acetic acid erbium, 1.5 mMs of second
Sour sodium, 6 milliliters of oleic acid are added in three-neck flask, under the protective condition of nitrogen, 150oAfter 1 hour being kept the temperature at a temperature of C,
8 milliliters of octadecylenes are added into three-neck flask, 155oContinue heat preservation 1 hour at a temperature of C, obtains clear solution B.Wait for that B is molten
After liquid naturally cools to room temperature, 8 milliliters of methanol solutions containing 2 mMs of ammonium fluorides are added dropwise in B solution, are then existed
80oC keeps the temperature half an hour.Wait for that methanol solution all after volatilization, is brought rapidly up to 270oC, and 60 minutes are kept the temperature at this temperature,
Then room temperature is naturally cooled to.It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by Yb/Er:Na3ZrF7It receives
Meter Jing is stored in spare in 4ml hexamethylenes.
4. being added to gained nanocrystal solution in 3 containing hydrochloric acid：Polyethyleneimine=1:In 5 mixed liquor, through ultrasound
72 hours, obtain the Yb/Er that amino is contained on surface:Na3ZrF7It is nanocrystalline.
5. gained in 2 and 4 is nanocrystalline with 2:1 ratio mixes in 10 ml deionized waters, is stirred at room temperature 48
Hour, freeze-dried acquisition fluoride nano crystal composite material.
Powder x-ray diffraction analysis：Synthesized precursor product is respectively hexagonal phase NaLuF4Nanocrystalline and tetragonal phase
Na3ZrF7It is nanocrystalline.Two kinds of presomas constitute nanocrystalline composite material through bond to surface.Ce/Tb:NaLuF4- Yb/
Er:Na3ZrF7Nanocrystalline composite material can generate bright green emission under the ultraviolet lamp shooting condition of 254nm wavelength.Ce/
Tb:NaLuF4- Yb/Er:Na3ZrF7Nanocrystalline composite material can generate bright under the laser shooting condition of 980nm wavelength
Simple spectrum band red emission.
Claims (8)
1. a kind of fluoride nano crystal composite material, which is characterized in that the composite material is by hexagonal phase NaGdF4It is nanocrystalline with it is cubic
Phase Na3HfF7Nanocrystalline two kinds of presomas are obtained using surface chemistry bonding action.
2. a kind of fluoride nano crystal composite material according to claim 1, which is characterized in that the hexagonal phase
NaGdF4Nanocrystalline and tetragonal phase Na3HfF7Nanocrystalline molar ratio is 3:1-1:3；Preferably 2:1-1:1.
3. a kind of fluoride nano crystal composite material according to claim 1, which is characterized in that surface chemistry bonding action
For the chemical bond of carboxyl and amino.
4. a kind of method preparing the fluoride nano crystal composite material described in claim 1 ~ 3 any one claim,
It is characterized in that, this approach includes the following steps：
1）Prepare the NaGdF that carboxyl is contained on surface4It is nanocrystalline；
2）Prepare the Na that amino is contained on surface3HfF7It is nanocrystalline；
3）Gained NaGdF4Nanocrystalline and Na3HfF7It is nanocrystalline with 3:1-1:3 molar ratio mixes in deionized water, in room
Temperature lower stirring 24-48 hours, freeze-dried acquisition fluoride nano crystal composite material.
5. according to the method described in claim 4, it is characterized in that, step 1）Include the following steps：
1）By 10-20% mole of acetic acid gadoliniums, 8-12 milliliters of oleic acid are added in three-neck flask, under the protective condition of inert gas,
After keeping the temperature 0.5 ~ 2 hour at a temperature of 150 ~ 170 DEG C, 12-16 milliliters of octadecylenes are added into three-neck flask, 150 ~ 170
After keeping the temperature 0.5 ~ 2 hour at a temperature of DEG C, clear solution A is obtained；
2）After solution A naturally cools to room temperature, contain 30-60% moles of ammonium fluoride and 10-30% moles of hydroxide by 5 ~ 7 milliliters
The methanol solution of sodium is added dropwise in solution A, then keeps the temperature 0.4 ~ 1 hour at 75 ~ 85 DEG C；
3）Wait for that methanol solution all after volatilization, is brought rapidly up 280-300 DEG C, and keep the temperature 90-120 minutes at this temperature,
Then room temperature is naturally cooled to；It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by NaGdF4Nanocrystalline guarantor
There are spare in hexamethylene；
4）By gained NaGdF4Nanocrystal solution is added to containing hydrochloric acid：Citric acid=1:5-1:In 20 mixed liquor, through ultrasound
24-48 hours, obtain the NaGdF that carboxyl is contained on surface4It is nanocrystalline.
6. according to the method described in claim 5, it is characterized in that, inert gas is one kind in nitrogen, neon, argon gas.
7. according to the method described in claim 4, it is characterized in that, step 2）Include the following steps：
1）By 10-20% moles of acetylacetone,2,4-pentanedione hafnium, 20-40% mole of acetic acid is received, and 6-8 milliliters of oleic acid are added in three-neck flask,
Under the protective condition of inert gas, after keeping the temperature 0.5 ~ 2 hour at a temperature of 140 ~ 160 DEG C, 8-12 is added into three-neck flask
Milliliter octadecylene, continues heat preservation 0.5 ~ 2 hour at a temperature of 150 ~ 160 DEG C, obtains clear solution B；
2）After B solution naturally cools to room temperature, 8 milliliters of methanol solutions containing 20-60% moles of ammonium fluoride are added dropwise to
In B solution, then 0.4 ~ 1 hour is kept the temperature at 75 ~ 85 DEG C；
3）Wait for that methanol solution all after volatilization, is brought rapidly up 250-270 DEG C, and keep the temperature 30-90 minutes at this temperature, so
After naturally cool to room temperature；It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by Na3HfF7Nanocrystalline preservation
It is spare in hexamethylene；
4）By the Na of gained3HfF7Nanocrystal solution is added to containing hydrochloric acid：Polyethyleneimine=1:5-1:In 20 mixed liquor,
Through 48-72 hours ultrasonic, the Na of amino is contained on acquisition surface3HfF7It is nanocrystalline.
8. the method according to the description of claim 7 is characterized in that inert gas is one kind in nitrogen, neon, argon gas.
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