CN105086999B - Polyacrylic acid modified spherical single dispersing NaGdF4:Yb3+,Er3+Up-conversion phosphor - Google Patents
Polyacrylic acid modified spherical single dispersing NaGdF4:Yb3+,Er3+Up-conversion phosphor Download PDFInfo
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Abstract
The invention discloses a kind of polyacrylic acid modified spherical single dispersing NaGdF4:Yb3+,Er3+The preparation method of up-conversion phosphor.Using hydro-thermal method, make surface modifier with polyacrylic acid, by adjusting NaF, NH4HF2Proportioning between rare earth ion total amount, realize spherical NaGdF4:Yb3+,Er3+The synthesis of up-conversion phosphor, and obtained fluorescent powder has monodispersity, this method preparation technology is simple, enriches NaGdF4:Yb3+,Er3+The form of expression of up-conversion fluorescence powder.Due to the spherical single dispersing NaGdF that specific surface area is larger4:Yb3+,Er3+The upper high conversion efficiency of fluorescent material, and the phosphor surface of polyacrylic acid parcel has hydrophilic radical, expands spherical single dispersing NaGdF4:Yb3+,Er3+Application prospect of the up-conversion phosphor in biomarker and organic and inorganic light-emitting Material Field.
Description
Technical field
The invention belongs to the rare earth luminescent material preparing technical field that surface is modified, and in particular to a kind of polyacrylic acid modified
Spherical single dispersing NaGdF4: Yb3+, Er3+The preparation method of up-conversion phosphor.
Background technology
Up-conversion phosphor using rare earth fluoride as matrix, because it is in nano photoelectronic devices, FPD, biology
The extensive and important application in the fields such as medical imaging, solid state laser and anti-counterfeiting technology, have become the heat of an investigation of materials
Point.In numerous rare earth luminescent materials, Yb3+、Er3+Double-doped NaLnF4It is the up-conversion luminescent material for most having application prospect,
By the common concern of domestic and foreign scholars（Nano Letters, 2004, 4(11): 2191-2196）.Wherein gadolinium fluoride sodium
（NaGdF4）Relatively low phonon energy, it is a kind of good luminous host with stable physical and chemical performance.And due to base
Matter cation Gd3+With good paramagnetism so that rear-earth-doped NaGdF4Nano material can be used as a kind of effective magnetic
Resonance image-forming contrast agent（Advanced Materials, 2010, 22(30): 3266-3271）.
At present, many methods are used for preparing Yb3+、Er3+Double-doped NaGdF4Nano particle, but most of be all
Using the surface modifier of the non-hydrophilics such as citric acid, oleic acid, synthesized up-conversion phosphor does not have hydrophily, and this is with regard to big
Its application in bioluminescence field is limited greatly, and polyacrylic acid is a kind of high molecular polymer with hydrophilic radical, usually
For rare earth ion doped NaYF4In the Research on Surface Modification of fluorescent material, Yb is modified using polyacrylic acid3+、Er3+Double-doped
NaGdF4Nano particle, thus it is possible to vary NaGdF4The group of nano grain surface, so as to improve its hydrophilicity, and polypropylene
Acid is often as a kind of dispersant, the characteristics of fluorescent powder grain so synthesized is also equipped with monodispersity, is expected to be used for organic-nothing
In the preparation field of machine laminated film.In addition, the pattern of fluorescent material has a great impact to the reprocessing in illumination effect and later stage,
It is close can to obtain higher accumulation because specific surface area is bigger than the fluorescent powder grain of other patterns for wherein spherical fluorescent powder grain
Degree, so as to reduce the scattering process of nano particle, obtain higher fluorescence conversion efficiency.Therefore, if by NaGdF4:
Yb3+, Er3+Surface be modified, make it have hydrophilic while can obtain spherical monodispersed pattern again, then
NaGdF4: Yb3+, Er3+To all have very in the preparation field of bioluminescence field or organic-inorganic composite film
Big application prospect.
The content of the invention
It is an object of the invention to provide a kind of polyacrylic acid modified spherical single dispersing NaGdF4: Yb3+, Er3+It is upper to turn
The preparation method of fluorescent material is changed, preparation technology is simple, enriches NaGdF4: Yb3+, Er3+The performance shape of up-conversion fluorescence powder
Formula.Due to the spherical single dispersing NaGdF that specific surface area is larger4: Yb3+, Er3+The upper high conversion efficiency of fluorescent material, and polypropylene
The phosphor surface of acid parcel has hydrophilic radical, expands spherical single dispersing NaGdF4: Yb3+, Er3+Up-conversion phosphor exists
The application prospect of biomarker and organic and inorganic field of light emitting materials.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of polyacrylic acid modified spherical single dispersing NaGdF4: Yb3+, Er3+The preparation method of up-conversion phosphor
Comprise the following steps that：
（1）By chemical formula NaGd1-x-yYbxEryF4, 0.10≤x≤0.25, Gd, Yb and Er's rubs in 0.01≤y≤0.05
You measure ratio, weigh gadolinium nitrate, ytterbium nitrate and erbium nitrate；
（2）With molar ratio computing, polyacrylic acid：Rare earth ion total amount=6：1000, gadolinium nitrate, ytterbium nitrate and erbium nitrate is molten
In polyacrylic acid solution, it is well mixed, obtains solution A；
（3）With molar ratio computing, NaF：Rare earth ion total amount：NH4HF2=1~3：1：5 ~ 7, by NaF and NH4HF2It is dissolved in ultrapure
In water, stir, obtain solution B；
（4）Solution A and solution B are well mixed, solution ph is adjusted to 9 with ammoniacal liquor, obtains solution C；
（5）It is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and seals after solution C is stirred, 160 ~ 220 DEG C
16 ~ 24h of hydro-thermal reaction, cools to room temperature with the furnace, obtains sediment；
（6）Obtained sediment is centrifuged, and alternately cleaned with absolute ethyl alcohol and ultra-pure water, dries, grinding, obtains
Polyacrylic acid modified spherical single dispersing NaGdF4: Yb3+, Er3+Up-conversion phosphor.
Preferably, step（1）In, 0.17≤x≤0.19,0.01≤y≤0.03 and x+y=0.2.Alternatively, step（1）
Rare earth nitrades, be rare earth nitrades powder product, or by by rare earth oxide be dissolved in nitric acid then again will
Rare earth nitrades powder made from solution drying, or directly rare earth oxide is dissolved in nitric acid, then heating makes nitre
The rare earth nitrate solution obtained again with pure water constant volume after sour volatilization completely.
Further, step（2）Polyacrylic acid mean molecule quantity be 100000, the quality percentage of polyacrylic acid solution
Number is 35%, density 1.14g/mL.
Preferably, step（3）The dosage of middle ultra-pure water is 10 ~ 20mL.
Preferably, step（5）Middle mixing time is 15 ~ 30 min, and reactor volume compactedness is 70% ~ 80%.
Further, step（6）The middle number alternately cleaned with absolute ethyl alcohol and ultra-pure water is three times.
Preferably, step（6）Middle drying time is 8 ~ 24h.
Compared with prior art, the technical effects of the invention are that：
（1）The polyacrylic acid modified spherical single dispersing NaGdF of the present invention4: Yb3+, Er3+The synthesis of up-conversion phosphor
Technique is simple, using hydro-thermal method, by adjusting NaF, NH4HF2Proportioning between rare earth ion total amount, realizes polyacrylic acid
Modified spherical NaGdF4: Yb3+, Er3+The synthesis of up-conversion phosphor, enriches NaGdF4: Yb3+, Er3+Upper conversion is glimmering
The pattern form of expression of light powder.
（2）The polyacrylic acid modified spherical single dispersing NaGdF of the present invention4: Yb3+, Er3+Up-conversion phosphor is using poly-
Acrylic acid has monodispersity as surface modifier, obtained fluorescent powder so that the NaGdF that surface is modified4: Yb3+,
Er3+Up-conversion phosphor has broad application prospects in the preparation of composite organic-inorganic material.
Brief description of the drawings
Fig. 1 is polyacrylic acid modified spherical single dispersing NaGdF prepared by the embodiment of the present invention 1 ~ 44: Yb3+, Er3+On
The XRD spectrum of conversion phosphor, it can be seen that obtained polyacrylic acid modified spherical single dispersing NaGdF4: Yb3 +, Er3+Up-conversion phosphor is the NaGdF of hexagonal phase4: Er3+, Yb3+；
Fig. 2 is polyacrylic acid modified spherical single dispersing NaGdF prepared by the embodiment of the present invention 14: Yb3+, Er3+It is upper to turn
Change the SEM image of fluorescent material；
Fig. 3 is polyacrylic acid modified spherical single dispersing NaGdF prepared by the embodiment of the present invention 24: Yb3+, Er3+It is upper to turn
Change the SEM image of fluorescent material；
Fig. 4 is polyacrylic acid modified spherical single dispersing NaGdF prepared by the embodiment of the present invention 34: Yb3+, Er3+It is upper to turn
Change the SEM image of fluorescent material；
Fig. 5 is polyacrylic acid modified spherical single dispersing NaGdF prepared by the embodiment of the present invention 44: Yb3+, Er3+It is upper to turn
Change the SEM image of fluorescent material.
Embodiment
Embodiment 1
1）3.2mL gadolinium nitrates, 1.7mL ytterbium nitrates, 0.3mL Nitrate Solutions are measured, is dissolved in 3mL polyacrylic acid solutions,
It is well mixed, obtain solution A；
2）0.084g NaF are weighed, are dissolved in 10mL ultra-pure waters, add 0.57g NH4HF2, stir, obtain solution B；
3）Solution A and B are well mixed, pH value is adjusted to 9 with ammoniacal liquor, obtains solution C；
4）Solution C is stirred into 15min, after be transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and seal, 200
At DEG C after hydro-thermal reaction 16h, room temperature is cooled to the furnace, obtain sediment；
5）Obtained sediment is centrifuged（Rotating speed is 8000r/min）, centrifugation time 5min, and use absolute ethyl alcohol
With ultra-pure water alternately cleaning 3 times, centrifuge, then the material cleaned is placed in 80 DEG C of baking ovens and dries 12h, grinding obtains
Polyacrylic acid modified spherical single dispersing NaGdF4: Yb3+, Er3+Up-conversion phosphor.
Embodiment 2
1）3.2mL gadolinium nitrates, 1.7mL ytterbium nitrates, 0.3mL Nitrate Solutions are measured, is dissolved in 3mL polyacrylic acid solutions,
It is well mixed, obtain solution A；
2）0.084g NaF are weighed, are dissolved in 10mL ultra-pure waters, add 0.799g NH4HF2, stir, obtain solution B；
3）Solution A and B are well mixed, pH value is adjusted to 9 with ammoniacal liquor, obtains solution C；
4）Solution C is stirred into 15min, after be transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and seal, 200
At DEG C after hydro-thermal reaction 16h, room temperature is cooled to the furnace, obtain sediment；
5）Obtained sediment is centrifuged（Rotating speed is 8000r/min）, centrifugation time 5min, and use absolute ethyl alcohol
With ultra-pure water alternately cleaning 3 times, centrifuge, then the material cleaned is placed in 80 DEG C of baking ovens and dries 12h, grinding obtains
Polyacrylic acid modified spherical single dispersing NaGdF4: Yb3+, Er3+Up-conversion phosphor.
Embodiment 3
1）3.2mL gadolinium nitrates, 1.7mL ytterbium nitrates, 0.3mL Nitrate Solutions are measured, is dissolved in 3mL polyacrylic acid solutions,
It is well mixed, obtain solution A；
2）0.252g NaF are weighed, are dissolved in 10mL ultra-pure waters, add 0.57g NH4HF2, stir, obtain solution B；
3）Solution A and B are well mixed, pH value is adjusted to 9 with ammoniacal liquor, obtains solution C；
4）Solution C is stirred into 15min, after be transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and seal, 200
At DEG C after hydro-thermal reaction 16h, room temperature is cooled to the furnace, obtain sediment；
5）Obtained sediment is centrifuged（Rotating speed is 8000r/min）, centrifugation time 5min, and use absolute ethyl alcohol
With ultra-pure water alternately cleaning 3 times, centrifuge, then the material cleaned is placed in 80 DEG C of baking ovens and dries 12h, grinding obtains
Polyacrylic acid modified spherical single dispersing NaGdF4: Yb3+, Er3+Up-conversion phosphor.
Embodiment 4
1）3.2mL gadolinium nitrates, 1.7mL ytterbium nitrates, 0.3mL Nitrate Solutions are measured, is dissolved in 3mL polyacrylic acid solutions,
It is well mixed, obtain solution A；
2）0.252g NaF are weighed, are dissolved in 10mL ultra-pure waters, add 0.799g NH4HF2, stir, obtain solution B；
3）Solution A and B are well mixed, pH value is adjusted to 9 with ammoniacal liquor, obtains solution C；
4）Solution C is stirred into 15min, after be transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and seal, 200
At DEG C after hydro-thermal reaction 16h, room temperature is cooled to the furnace, obtain sediment；
5）Obtained sediment is centrifuged（Rotating speed is 8000r/min）, centrifugation time 5min, and use absolute ethyl alcohol
With ultra-pure water alternately cleaning 3 times, centrifuge, then the material cleaned is placed in 80 DEG C of baking ovens and dries 12h, grinding obtains
Polyacrylic acid modified spherical single dispersing NaGdF4: Yb3+, Er3+Up-conversion phosphor.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (6)
- A kind of 1. polyacrylic acid modified spherical single dispersing NaGdF4: Yb3+, Er3+The preparation method of up-conversion phosphor, it is special Sign is：Comprise the following steps that：（1）By chemical formula NaGd1-x-yYbxEryF4, 0.10≤x≤0.25, Gd, Yb and Er mole meter in 0.01≤y≤0.05 Ratio is measured, weighs gadolinium nitrate, ytterbium nitrate and erbium nitrate；（2）With molar ratio computing, polyacrylic acid：Rare earth ion total amount=6：1000, gadolinium nitrate, ytterbium nitrate and erbium nitrate are dissolved in poly- In acrylic acid solution, it is well mixed, obtains solution A；（3）With molar ratio computing, NaF：Rare earth ion total amount：NH4HF2=1~3：1：5 ~ 7, by NaF and NH4HF2It is dissolved in ultra-pure water, Stir, obtain solution B；（4）Solution A and solution B are well mixed, solution ph is adjusted to 9 with ammoniacal liquor, obtains solution C；（5）It is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and seals after solution C is stirred, 160 ~ 220 DEG C of hydro-thermals 16 ~ 24h is reacted, room temperature is cooled to the furnace, obtains sediment；（6）Obtained sediment is centrifuged, and alternately cleaned with absolute ethyl alcohol and ultra-pure water, dries, grinding, obtains poly- third The spherical single dispersing NaGdF that olefin(e) acid is modified4: Yb3+, Er3+Up-conversion phosphor.
- 2. according to the method for claim 1, it is characterised in that：Step（1）Rare earth nitrades, be rare earth nitrades powder Finished product, or by by rare earth oxide be dissolved in nitric acid then again by solution dry made from rare earth nitrades powder, Either directly rare earth oxide is dissolved in nitric acid, then heating makes nitric acid be obtained again with pure water constant volume after volatilizing completely Rare earth nitrate solution.
- 3. according to the method for claim 1, it is characterised in that：Step（2）The mean molecule quantity of polyacrylic acid be 100000, the mass percent of polyacrylic acid solution is 35%, density 1.14g/mL.
- 4. according to the method for claim 1, it is characterised in that：Step（3）In ultrapure water consumption be 10 ~ 20mL.
- 5. according to the method for claim 1, it is characterised in that：Step（5）Middle mixing time is 15 ~ 30 minutes, reactor Volume compactedness is 70% ~ 80%.
- 6. according to the method for claim 1, it is characterised in that：Step（6）Drying time be 8 ~ 24h.
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| CN106086173B (en) * | 2016-06-14 | 2019-12-24 | 西安交通大学 | Rapid bacteria detection method based on up-conversion fluorescence resonance energy transfer |
| CN110746972B (en) * | 2019-10-22 | 2022-06-14 | 岭南师范学院 | Preparation method of calcium-doped fluorescence-enhanced water-soluble NaErF4 Yb red light up-conversion nano material |
| CN115557528A (en) * | 2022-09-29 | 2023-01-03 | 广州工程技术职业学院 | Rare earth doped up-conversion luminescent powder and preparation method thereof |
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| CN101525540A (en) * | 2009-04-08 | 2009-09-09 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing fluorescent nano material converted on NaYF4 |
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| CN101525540A (en) * | 2009-04-08 | 2009-09-09 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing fluorescent nano material converted on NaYF4 |
Non-Patent Citations (2)
| Title |
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| Surface ligand-mediated phase and upconversion luminescence tuning of multifunctional NaGdF4:Yb/Er materials with paramagnetic and cathodoluminescent characteristics;Ming-Kiu Tsang等;《Optical Materials》;20131231;第35卷;2691–2697 * |
| Upconversion Luminescence Properties of Ho3+ , Tm3 + , Yb3 + Co-Doped Nanocrystal NaYF4 Synthesized by Hydrothermal Method;Yang Kuisheng等;《JOURNAL OF RARE EARTHS》;20061231;757-760 * |
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