CN108531184A - A kind of polychrome composite nano materials and preparation method thereof of multiband excitation - Google Patents
A kind of polychrome composite nano materials and preparation method thereof of multiband excitation Download PDFInfo
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Abstract
The invention belongs to field of inorganic materials, are related to a kind of polychrome composite nano materials and preparation method thereof of multiband excitation.A kind of polychrome composite nano materials of multiband excitation, the composite material is by Ce/Tb (Eu):NaGdF4 is nanocrystalline and Yb/Ho:Na3ZrF7Nanocrystalline two kinds of presomas are obtained using surface chemistry bonding action.This composite Nano crystal composite material by upper by converting from lower conversion luminescence rare earth ion doping in different matrix, to inhibit the radiationless cross relaxation process between rare earth ion, and the multicolor luminous characteristic of efficient multiband excitation may be implemented, which is expected to obtain practical application in multi-modality imaging and optical anti-counterfeiting field.
Description
Technical field
The invention belongs to field of inorganic materials, it is related to polychrome composite nano materials and its preparation side of a kind of multiband excitation
Method.
Background technology
Rare earth ion energy level is very abundant, the different characteristics of luminescences may be implemented in different basis materials, such as logical
It crosses crystal structure regulation and control and controllable transmitting of the erbium ion from green light to feux rouges may be implemented, this is advantageously implemented multicolor luminous.And structure
Nanocrystalline composite material is built, the flexible modulation of excitation wavelength and launch wavelength may be implemented, i.e., multiband excitation is multicolor luminous.
This multicolor luminous nanocomposite dependent on excitation wavelength has in multimode bio-imaging and fluorescence falsification preventing TAG field
Good application prospect.Although may be implemented by the method that a variety of rare earth ions are co-doped with it is multicolor luminous, due to rare earth from
Radiationless cross relaxation between son increased dramatically with the increase of ionic species and concentration, eventually lead to extremely low fluorescence effect
Rate is unfavorable for practical application.
Invention content
It is an object of the present invention to provide a kind of polychrome composite nano materials of multiband excitation, which adopts
With Ce/Tb (Eu):NaGdF4Nanocrystalline and Yb/Ho:Na3ZrF7Nanocomposite, this composite Nano crystal composite material pass through
By upper conversion from lower conversion luminescence rare earth ion doping in different matrix, to inhibit the radiationless friendship between rare earth ion
Relaxation process is pitched, and the multicolor luminous characteristic of efficient multiband excitation may be implemented, which is expected in multi-modality imaging
Practical application is obtained with optical anti-counterfeiting field.Second object of the present invention is to provide the preparation method of above-mentioned composite material,
This method is at low cost, yield is high, and 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 polychrome composite nano materials of multiband excitation, the composite material is by Ce/Tb (Eu):NaGdF4 is nanocrystalline and Yb/
Ho:Na3ZrF7Nanocrystalline two kinds of presomas are obtained using surface chemistry bonding action.
Preferably, the Ce/Tb (Eu):NaGdF4 is nanocrystalline and Yb/Ho:Na3ZrF7Nanocrystalline molar ratio is 3:
1-1:3；Preferably 2:1-1:1.
Preferably, the Ce/Tb (Eu):The molar ratio of NaGdF4 nanocrystalline middle Gd, Ce, Tb (Eu) is 10 ~ 20:
2~40.5~2；Yb/Ho:Na3ZrF7The molar ratio of nanocrystalline middle Zr, Yb, Ho are 10 ~ 20:2~40.5~2.
Preferably, the surface chemistry bonding action is the chemical bond of carboxyl and amino.
In order to realize second above-mentioned purpose, present invention employs technical solutions below：
A method of the polychrome composite nano materials of the multiband excitation being prepared, this approach includes the following steps：
1）Prepare the Ce/Tb (Eu) that carboxyl is contained on surface:NaGdF4 is nanocrystalline；
2）Prepare the Yb/Ho that amino is contained on surface:Na3ZrF7 is nanocrystalline；
3）Gained Ce/Tb (Eu):NaGdF4 is nanocrystalline and Yb/Ho:Na3ZrF7 is nanocrystalline with 3:1-1:3 molar ratio is being gone
It mixes, is stirred at room temperature 24-48 hours in ionized water, the freeze-dried polychrome composite Nano material for obtaining multiband excitation
Material.
Preferably, the step 1）Include the following steps：
1）By (10-20) % mole of acetic acid gadoliniums, (2-4) % mole of acetic acid ceriums, (0.5-2) % mole of acetic acid terbiums（Or acetic acid europium）With (8-
12) milliliter oleic acid is added in three-neck flask, and under the protective condition of inert gas, 0.5 is kept the temperature at a temperature of 150 ~ 170 DEG C
After ~ 2 hours, 12-16 milliliters of octadecylenes are added into three-neck flask, after keeping the temperature 0.5 ~ 2 hour at a temperature of 150 ~ 170 DEG C,
Obtain clear solution A；
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 Ce/Tb (Eu):
NaGdF4 is nanocrystalline be stored in it is spare in hexamethylene；
4）By gained Ce/Tb (Eu):NaGdF4 nanocrystal solutions are added to containing hydrochloric acid：Citric acid=1:5-1:20 mixed liquor
In, through 24-48 hours ultrasonic, the Ce/Tb (Eu) of carboxyl is contained on acquisition surface:NaGdF4 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, (2-4) % mole of acetic acid ytterbiums, (0.5-2) % mole of acetic acid holmiums, (20-40) % rubs
That sodium acetate, (6-8) milliliter oleic acid is added in three-neck flask, under the protective condition of inert gas, in 140 ~ 160 DEG C of temperature
After the lower heat preservation of degree 0.5 ~ 2 hour, 8-12 milliliters of octadecylenes are added into three-neck flask, after continuation of insurance at a temperature of 150 ~ 160 DEG C
Temperature 0.5 ~ 2 hour, 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 Yb/Ho:Na3ZrF7 nanometers
Crystalline substance is stored in spare in hexamethylene；
4）By the Yb/Ho of gained:Na3ZrF7 nanocrystal solutions are added to containing hydrochloric acid：Polyethyleneimine=1:5-1:20 it is mixed
It closes in liquid, through 48-72 hours ultrasonic, the Yb/Ho of amino is contained on acquisition surface:Na3ZrF7 is nanocrystalline.
Preferably, the inert gas is one kind in nitrogen, neon, argon gas.
The present invention can also replace Yb/Ho using Hf:Zr during Na3ZrF7 is nanocrystalline.
The present invention obtains polychrome composite nano materials powder x-ray diffraction analysis and shows：Gained presoma is respectively six sides
Phase NaGdF4Nanocrystalline and tetragonal phase Na3ZrF7It is nanocrystalline, include hexagonal phase NaGdF simultaneously in composite material4With tetragonal phase
Na3ZrF7.Spectroscopic analysis results show the composite material, under the laser shooting condition of 980nm, generate Ho3+Yellow light hair
It penetrates, when with the ultraviolet excitation of 254nm, obtains Tb3+Green emission or Eu3+Red emission.
Nanocrystalline composite material of the present invention is characterized in that, first respectively sends out upper conversion with lower conversion
Light rare earth ion is doped to respectively in different nanocrystalline systems, to significantly inhibit the radiationless intersection between rare earth ion
Relaxation process obtains efficient fluorescent emission；Secondly by rare earth ion of the selection with the different characteristics of luminescences, realize not
With obtained under the conditions of excitation wavelength different colours shine；Finally, this nanocrystalline composite material is advantageously implemented multi-modality imaging
With the fluorescence falsification preventing of high security.
The present invention's additionally provides a kind of anti-counterfeiting ink, the water for the polychrome composite nano materials that the multiband is excited
Solution add or do not add ink conventional material as fluorescent ink be directly used in printing with it is hand-written.Print or it is hand-written go out
Image is visible in the UV lamp.
The present invention's additionally provides a kind of biomarker, the polychrome composite Nano material for using above-mentioned multiband to excite
Material.
The polychrome composite nano materials of above-mentioned multiband excitation can also be applied to cell and the separation of biomolecule is pure
Change.
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 the polychrome composite nano materials of this novel multiband excitation is expected to
It is widely used in nano material synthesis field.
Description of the drawings
Ce/Tb in Fig. 1, example 1:NaGdF4Nanocrystalline X-ray diffractogram.
Yb/Ho in Fig. 2, example 1:Na3ZrF7Nanocrystalline X-ray diffractogram.
Ce/Tb in Fig. 3, example 1:NaGdF4- Yb/Ho:Na3ZrF7The X-ray diffractogram of nanocrystalline composite material.
Ce/Tb in Fig. 4, example 1:NaGdF4- Yb/Ho:Na3ZrF7Nanocrystalline composite material is ultraviolet 254nm wavelength
Down-conversion fluorescent spectrogram under lamp shooting condition.
Ce/Tb in Fig. 5, example 1:NaGdF4- Yb/Ho:Na3ZrF7Laser of the nanocrystalline composite material in 980nm wavelength
Up-conversion fluorescence spectrogram under device shooting condition.
Ce/Eu in Fig. 6, example 2:NaGdF4- Yb/Ho:Na3ZrF7Nanocrystalline composite material is ultraviolet 254nm wavelength
Down-conversion fluorescent spectrogram under lamp shooting condition.
Specific implementation mode
Embodiment 1:
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:In 10 mixed liquor, through 48 hours ultrasonic,
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:It is small through ultrasound 72 in 5 mixed liquor
When, 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. 1）With four
Square phase Na3ZrF7It is nanocrystalline（Fig. 2）；Fig. 3 shows that two kinds of presomas constitute nanocrystalline composite material through bond to surface；Fig. 4
Show Ce/Tb:NaGdF4- Yb/Ho:Na3ZrF7Nanocrystalline composite material can produce under the ultraviolet lamp shooting condition of 254nm wavelength
Raw bright green emission；Fig. 5 shows Ce/Tb:NaGdF4- Yb/Ho:Na3ZrF7Nanocrystalline composite material is in 980nm wavelength
Bright yellow emission can be generated under laser shooting condition.
Embodiment 2
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:In 10 mixed liquor, through 48 hours ultrasonic,
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.
Fig. 6 shows Ce/Eu:NaGdF4- Yb/Ho:Na3ZrF7Burst of ultraviolel of the nanocrystalline composite material in 254nm wavelength
Under the conditions of can generate bright red emission.
Claims (9)
1. a kind of polychrome composite nano materials of multiband excitation, which is characterized in that the composite material is by Ce/Tb (Eu):NaGdF4
Nanocrystalline and Yb/Ho:Na3ZrF7Nanocrystalline two kinds of presomas are obtained using surface chemistry bonding action.
2. a kind of polychrome composite nano materials of multiband excitation according to claim 1, which is characterized in that described
Ce/Tb(Eu):NaGdF4Nanocrystalline and Yb/Ho:Na3ZrF7Nanocrystalline molar ratio is 3:1-1:3；Preferably 2:1-1:1.
3. a kind of polychrome composite nano materials of multiband excitation according to claim 1, which is characterized in that Ce/Tb
(Eu):NaGdF4The molar ratio of nanocrystalline middle Gd, Ce, Tb (Eu) is 10 ~ 20:2~40.5~2；Yb/Ho:Na3ZrF7It is nanocrystalline
The molar ratio of middle Zr, Yb, Ho are 10 ~ 20:2~40.5~2.
4. a kind of polychrome composite nano materials of multiband excitation according to claim 1, which is characterized in that surface chemistry
Bonding action is the chemical bond of carboxyl and amino.
5. a kind of polychrome composite nano materials of the multiband excitation prepared described in claim 1 ~ 4 any one claim
Method, which is characterized in that this approach includes the following steps：
1）Prepare the Ce/Tb (Eu) that carboxyl is contained on surface:NaGdF4It is nanocrystalline；
2）Prepare the Yb/Ho that amino is contained on surface:Na3ZrF7It is nanocrystalline；
3）Gained Ce/Tb (Eu):NaGdF4 is nanocrystalline and Yb/Ho:Na3ZrF7 is nanocrystalline with 3:1-1:3 molar ratio is being gone
It mixes, is stirred at room temperature 24-48 hours in ionized water, the freeze-dried polychrome composite Nano material for obtaining multiband excitation
Material.
6. according to the method described in claim 2, it is characterized in that, step 1）Include the following steps：
1）By (10-20) % mole of acetic acid gadoliniums, (2-4) % mole of acetic acid ceriums, (0.5-2) % mole of acetic acid terbiums（Or acetic acid europium）With (8-
12) milliliter oleic acid is added in three-neck flask, and under the protective condition of inert gas, 0.5 is kept the temperature at a temperature of 150 ~ 170 DEG C
After ~ 2 hours, 12-16 milliliters of octadecylenes are added into three-neck flask, after keeping the temperature 0.5 ~ 2 hour at a temperature of 150 ~ 170 DEG C,
Obtain clear solution A；
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 Ce/Tb (Eu):
NaGdF4 is nanocrystalline be stored in it is spare in hexamethylene；
4）By gained Ce/Tb (Eu):NaGdF4 nanocrystal solutions are added to containing hydrochloric acid：Citric acid=1:5-1:20 mixed liquor
In, through 24-48 hours ultrasonic, the Ce/Tb (Eu) of carboxyl is contained on acquisition surface:NaGdF4 is nanocrystalline.
7. according to the method described in claim 6, it is characterized in that, inert gas is one kind in nitrogen, neon, argon gas.
8. according to the method described in claim 5, it is characterized in that, step 2）Include the following steps：
1）By (10-20) % moles of acetylacetone,2,4-pentanedione zirconium, (2-4) % mole of acetic acid ytterbiums, (0.5-2) % mole of acetic acid holmiums, (20-40) % rubs
That sodium acetate, (6-8) milliliter oleic acid is added in three-neck flask, under the protective condition of inert gas, in 140 ~ 160 DEG C of temperature
After the lower heat preservation of degree 0.5 ~ 2 hour, 8-12 milliliters of octadecylenes are added into three-neck flask, after continuation of insurance at a temperature of 150 ~ 160 DEG C
Temperature 0.5 ~ 2 hour, 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 Yb/Ho:Na3ZrF7 nanometers
Crystalline substance is stored in spare in hexamethylene；
4）By the Yb/Ho of gained:Na3ZrF7 nanocrystal solutions are added to containing hydrochloric acid：Polyethyleneimine=1:5-1:20 it is mixed
It closes in liquid, through 48-72 hours ultrasonic, the Yb/Ho of amino is contained on acquisition surface:Na3ZrF7 is nanocrystalline.
9. according to the method described in claim 8, it is characterized in that, inert gas is one kind in nitrogen, neon, argon gas.
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Cited By (3)
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| CN110055070A (en) * | 2019-04-28 | 2019-07-26 | 中国计量大学 | A kind of Ratio-type green emission fluorescent material |
| CN110157433A (en) * | 2019-04-26 | 2019-08-23 | 中国计量大学 | A kind of Ratio-type yellow light turns blue emission fluorescent material and its application as Ratio-type fluorescent pH probe |
| CN113072939A (en) * | 2020-01-03 | 2021-07-06 | 中国科学院福建物质结构研究所 | In-vivo degradable up-conversion inorganic nano material and preparation method and application thereof |
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| CN110157433A (en) * | 2019-04-26 | 2019-08-23 | 中国计量大学 | A kind of Ratio-type yellow light turns blue emission fluorescent material and its application as Ratio-type fluorescent pH probe |
| CN110157433B (en) * | 2019-04-26 | 2021-11-19 | 中国计量大学 | Ratio type yellow light-to-blue light emission fluorescent material and application thereof as ratio type fluorescent pH probe |
| CN110055070A (en) * | 2019-04-28 | 2019-07-26 | 中国计量大学 | A kind of Ratio-type green emission fluorescent material |
| CN110055070B (en) * | 2019-04-28 | 2021-11-19 | 中国计量大学 | Ratio type green light emission fluorescent material |
| CN113072939A (en) * | 2020-01-03 | 2021-07-06 | 中国科学院福建物质结构研究所 | In-vivo degradable up-conversion inorganic nano material and preparation method and application thereof |
| CN113072939B (en) * | 2020-01-03 | 2022-07-19 | 中国科学院福建物质结构研究所 | In vivo degradable up-conversion inorganic nano material and preparation method and application thereof |
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