CN114736683A - Orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity and preparation method thereof - Google Patents

Orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity and preparation method thereof Download PDF

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CN114736683A
CN114736683A CN202210333614.6A CN202210333614A CN114736683A CN 114736683 A CN114736683 A CN 114736683A CN 202210333614 A CN202210333614 A CN 202210333614A CN 114736683 A CN114736683 A CN 114736683A
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rare earth
nayf
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张桂龙
刘璐
李文玲
田梗
魏鹏飞
杨春华
姜文国
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Binzhou Medical College
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Abstract

The invention discloses an orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity and a preparation method thereof, wherein the preparation method comprises the following steps: (1) synthesis of NaYF45% Nd nanocrystal core; (2) mixing trifluoroacetate, oleic acid and octadecene of rare earth elements, removing water and oxygen in vacuum, introducing protective gas, and performing microwave reaction to obtain rare earth element-OA; c is to be2F3NaO2Mixing with oleic acid, and performing microwave reaction to obtain Na-TFA-OA; (3) performing at least one shell growth: forming a core layer NaYF4Mixing a cyclohexane solution with 5 percent of Nd with oleic acid, octadecene, rare earth elements-OA and Na-TFA-OA, removing cyclohexane in vacuum, introducing protective gas, and carrying out microwave reaction at the temperature of 250 ℃ and 260 ℃ for 50-60min to obtain the Nd-Fe-B-O-doped barium niobate. The invention shortens the reaction time, has simple preparation process and low material costLow, high product phase purity and excellent orthogonal fluorescence emission performance.

Description

Orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity and preparation method thereof
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to an orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity and a preparation method thereof.
Background
The optical imaging technology has the advantages of no wound, safety, strong visualization capability, high spatial resolution, low cost and the like, can perform real-time and multidimensional visual monitoring on biomolecules, cells, tissues and organisms, and is an important research means in the field of biomedicine. Among them, near-infrared live imaging has numerous advantages: compared with the imaging methods such as X-ray, nuclear magnetic resonance, ultrasound and the like which are commonly used in clinic, near-infrared optical imaging, especially near-infrared two-region fluorescence imaging, has the advantages of high spatial resolution, low self-body biological fluorescence background, strong tissue penetration capability and the like, and as one of near-infrared inorganic nano probes, the rare earth nano material has larger Stokes shift, minimum photobleaching, narrow and multi-peak emission characteristics and negligible excitation-emission band overlapping, and the lanthanide rare earth nano material is widely applied as a fluorescence probe. The emission wavelength of the nanoparticle can be tuned and the luminescence life can be prolonged by doping different rare earth metal ions, and an up/down conversion (D/UCNP) orthogonal luminescence nano composite material can be synthesized by doping Er and Nd.
The low photobleaching is a remarkable characteristic that lanthanide-doped rare earth nanoparticles are used as a luminescent probe, the wavelength conversion capability of the rare earth nanomaterial can be used for designing a drug carrier for photodynamic therapy or a photoisomerization process, and meanwhile, the rare earth upconversion nanoparticles can also be used as a fluorescent probe for monitoring in-vivo distribution and metabolism of drugs by utilizing the excellent near-infrared fluorescence imaging performance. For lanthanide ion doped inorganic materials, the fluorescence properties largely depend on the parameters of the material such as composition, crystallinity, size and shape, and the like, and the traditional method for preparing rare earth nanocrystals mainly adopts a solid-phase reaction method, which has the disadvantages of complex process, high cost, single post-treatment method, low product phase purity and narrow doping range. Therefore, there is an urgent need to develop a method for preparing a near-infrared fluorescent nanoprobe with simple synthesis process, low cost and strong tissue penetration capability.
Disclosure of Invention
Aiming at the prior art, the invention provides a preparation method of an orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity, which aims to solve the problems of complex process, high cost, single post-treatment method, low product phase purity, narrow doping range and the like of the traditional preparation method.
In order to achieve the purpose, the invention adopts the technical scheme that: the orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity and the preparation method thereof are provided, and the preparation method comprises the following steps:
(1) synthesis of NaYF 45% Nd nanocrystal core;
(2) microwave synthesis of precursors of rare earth element-OA and Na-TFA-OA: mixing trifluoroacetate, oleic acid and octadecene of rare earth elements, removing water and oxygen in vacuum, introducing protective gas, and performing microwave reaction at the temperature of 120-130 ℃ for 40-50min to obtain rare earth element-OA; c is to be2F3NaO2Mixing with oleic acid, and performing microwave reaction at 60-70 deg.C for 40-50min to obtain Na-TFA-OA;
(3) performing at least one-time shell layer growth by adopting a continuous layer-by-layer growth method to prepare the rare earth nanocrystalline with the core-shell structure: forming a core layer NaYF4Mixing a cyclohexane solution with 5 percent of Nd with oleic acid, octadecene, rare earth elements-OA and Na-TFA-OA, removing cyclohexane in vacuum, introducing protective gas, and carrying out microwave reaction at the temperature of 250 ℃ and 260 ℃ for 50-60min to obtain the Nd-Fe-B-O-doped barium niobate.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, NaYF4The synthesis of the 5 percent Nd nanocrystal comprises the following steps: mixing Y (CF)3CO2)3·4H2O、Nd(CF3CO2)3·4H2Mixing O, octadecene and oleic acid, removing water and oxygen in vacuum, introducing argon, reacting at the temperature of 120-130 ℃ for 40-60min, cooling to the temperature of 50-60 ℃, adding NaOH and NH4Reacting the methanol solution of F for 50-60min, introducing nitrogen for protection, carrying out microwave reaction at 250-260 ℃ for 1-2h, and cooling to room temperature to obtain the catalyst.
Further, Y (CF)3CO2)3·4H2O、Nd(CF3CO2)3·4H2The dosage ratio of O, octadecene and oleic acid is 0.95-0.98 mol: 0.02-0.05 mol: 12-15L: 6 to 8L.
Further, the dosage ratio of trifluoroacetate, oleic acid and octadecene of rare earth elements is 6 mol: 24-26L: 34-36L.
Further, C2F3NaO2And oleic acid in a ratio of 40 mol: 50L.
Further, the rare earth element-OA is Gd-OA; the rare earth nanocrystalline with the core-shell structure is NaYF4:5％Nd@NaGdF4The preparation method comprises the following steps: forming a core layer NaYF4Mixing a cyclohexane solution with 5 percent of Nd with oleic acid, octadecene, Gd-OA and Na-TFA-OA, removing cyclohexane in vacuum, introducing argon, and carrying out microwave reaction at the temperature of 250-260 ℃ for 50-60min to obtain the Nd-Fe-B-based catalyst.
Further, the rare earth element-OA also comprises Yb-OA and Er-OA; the rare earth nanocrystalline with the core-shell structure is NaYF4:5％Nd@NaGdF4@NaYbF4The preparation method comprises the following steps: forming a core layer NaYF4:5％Nd@NaGdF4Mixing the cyclohexane solution with oleic acid, octadecene, Yb-OA, Er-OA and Na-TFA-OA, removing cyclohexane in vacuum, introducing argon, and performing microwave reaction at 250-260 ℃ for 50-60min to obtain the composite material.
Further, the rare earth element-OA also includes Y-OA; the rare earth nanocrystalline with the core-shell structure is NaYF4:5％Nd@NaGdF4@NaYbF4：2％Er@NaYF4The preparation method comprises the following steps: forming a core layer NaYF4:5％Nd@NaGdF4@NaYbF4Mixing the cyclohexane solution with oleic acid, octadecene, Y-OA and Na-TFA-OA, removing cyclohexane in vacuum, introducing argon, and carrying out microwave reaction at the temperature of 250-260 ℃ for 50-60min to obtain the compound.
The method firstly utilizes neodymium (Nd) to dope NaYF4Particles to form NaYF with down-conversion function 45% Nd nanocrystal core, followed by a shell layer of NaGdF4、NaYF4、NaYbF4: 2% Er in NaYF4Surface growth of 5% Nd nanocrystal coreOrthogonal fluorescence emission NaYF with adjustable excitation light intensity4:5％Nd@NaGdF4@NaYbF4:2％Er@NaYF4The rare earth nanocrystalline with the four-layer core-shell structure can achieve the purpose of optimizing the thickness of a shell layer and the size of nanoparticles by adjusting the amount of the dropwise added precursor Y-OA.
Further, NaYF4The ratio of the 5% Nd solution in cyclohexane to oleic acid, octadecene, rare earth elements-OA and Na-TFA-OA is 0.25 mol: 4-6L: 6-9L: 5-20L: 1.25-5L.
The invention also provides the orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity prepared by the preparation method.
The beneficial effects of the invention are:
1. the orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity combines strong near-infrared tissue penetrability and good biological safety, and shows excellent orthogonal fluorescence luminous performance;
2. the preparation method controls the size, the morphology and the luminescent property of the rare earth doped nanocrystal by controlling the reaction temperature, the amount of the reaction solvent, the reaction time and the like, utilizes a microwave synthesizer, shortens the reaction time, and has simple preparation process, low cost of used materials and high phase purity of products;
3. the rare earth fluoride used in the invention has low biological toxicity, and the synthesis of the near-infrared orthogonal fluorescence emission nanocrystalline with adjustable excitation light intensity improves the application range of near-infrared light.
Drawings
FIG. 1 is a transmission electron microscope image of core-shell structure nanocrystals obtained in example 1 of the present invention (core/core-shell mass ratios are 1: 2, 1: 2: 2, and 1: 2: 2: 4, respectively, correspond to TEM images);
FIGS. 2 and 3 are respectively core-shell nanocrystals NaYF obtained in example 1 of the present invention4:5％Nd@NaGdF4@NaYbF4:2％Er@NaYF4Emission spectra under 808nm and 980nm excitation;
FIG. 4 is a transmission electron microscope image of core-shell structure nanocrystals obtained in example 2 of the present invention (core/core-shell mass ratios are 1: 2, 1: 2: 2, and 1: 2: 2: 6, respectively, correspond to TEM images);
FIGS. 5 and 6 are respectively core-shell nanocrystals NaYF obtained in example 2 of the present invention4:5％Nd@NaGdF4@NaYbF4:2％Er@NaYF4Emission spectra under 808nm and 980nm excitation;
FIG. 7 is a transmission electron microscope image of core-shell structure nanocrystals obtained in example 3 of the present invention (core/core-shell mass ratios are 1: 2, 1: 2: 2, and 1: 2: 2: 8, respectively, correspond to TEM images);
FIGS. 8 and 9 are respectively core-shell nanocrystals NaYF obtained in example 3 of the present invention4:5％Nd@NaGdF4@NaYbF4:2％Er@NaYF4Emission spectra under 808nm and 980nm light excitation.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
Example 1
An orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity is prepared by the following steps:
(1) microwave synthesis of NaYF 45% of Nd nano-crystal: 0.95mmol of Y (CF)3CO2)3·4H2O、0.05mmol Nd(CF3CO2)3·4H2Mixing O, 12.0mL octadecene and 6.0mL oleic acid, removing water and oxygen in vacuum, introducing argon, transferring to a microwave synthesizer, heating to 130 deg.C for 20min, maintaining for 40min, cooling to 50 deg.C, adding a solution containing 2.5mmol NaOH and 4mmol NH4Reacting 6mL of methanol solution of F for 1h, introducing pure nitrogen for protection, heating to 260 ℃ by using microwaves for 20min, keeping for 1h, cooling to room temperature, and collecting nanoparticles to obtain the compound I;
(2) microwave synthesis of precursors Gd-OA and NaTFA-OA: taking 6mmol of Gd (CF)3CO2)3·4H2Adding 24ml of oleic acid and 36ml of octadecene into a 100ml three-neck flask, then removing water and oxygen in vacuum, introducing pure argon for protection, heating to 120 ℃ by using a microwave synthesizer for 10min, and reacting for 50min to obtain Gd-OA; take 40mmol of C2F3NaO2(Na-TFA) and 50ml oleic acid in a single-neck flask, transferred to a microwave ovenHeating to 60 deg.C for 10min, and reacting for 50min to obtain Na-TFA-OA;
(3) microwave synthesis of NaYF by continuous layer-by-layer growth method4:5％Nd@NaGdF4: mixing 4.0mL of oleic acid and 6.0mL of octadecene, adding a cyclohexane solution containing 0.25mmol of NaYF4: 5% Nd, 5mL of Gd-OA and 1.25mL of Na-TFA-OA mixed precursor solution, removing cyclohexane in vacuum, introducing argon, transferring to a microwave synthesizer, heating to 250 ℃ for 10min, and reacting for 60min to obtain the nano-crystalline solid phase material;
(4) adopting a continuous layer-by-layer growth method to synthesize NaYF by microwave4:5％Nd@NaGdF4@NaYbF42% Er: mixing 4.0mL of oleic acid with 6.0mL of octadecene, and adding a mixture containing 0.25mmol of NaYF4:Nd@NaGdF4The preparation method comprises the following steps of (1) removing cyclohexane in vacuum, introducing argon, transferring to a microwave synthesizer, heating to 260 ℃ for 15min, and reacting for 55min to obtain the mixed precursor solution of 6.25mL of Yb-OA, Er-OA and Na-TFA-OA (wherein the preparation methods of Yb-OA and Er-OA are the same as those of Gd-OA, and the volume ratio of Yb-OA to Er-OA to Na-TFA-OA is 3.92:0.08: 1);
(5) microwave synthesis of NaYF by continuous layer-by-layer growth method4:5％Nd@NaGdF4@NaYbF4：2％Er@NaYF4: mixing 4.0mL of oleic acid with 6.0mL of octadecene, and adding a mixture containing 0.25mmol of NaYF4:5％Nd@NaGdF4@NaYbF4The preparation method comprises the following steps of mixing a cyclohexane solution of 2% Er, 10mL of Y-OA (Gd-OA is used as the preparation method) and 2.5mL of Na-TFA-OA mixed precursor solution, removing cyclohexane in vacuum, introducing argon, transferring to a microwave synthesizer, heating to 260 ℃ for 10min, and reacting for 50min to obtain the material.
Example 2
An orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity is prepared by the following steps:
(1) microwave synthesis of NaYF 45% of Nd nanocrystalline: 0.98mmol of Y (CF)3CO2)3·4H2O、0.02mmol Nd(CF3CO2)3·4H2Mixing O, 13.0mL of octadecene and 7.0mL of oleic acid, removing water and oxygen in vacuum, introducing argon, transferring to a microwave synthesizer, and heating for 10minMaintaining at 120 deg.C for 60min, cooling to 55 deg.C, adding a solution containing 2.5mmol NaOH and 4mmol NH4Reacting 5mL of methanol solution of F for 50min, introducing pure argon for protection, heating to 255 ℃ by microwave for 15min, keeping for 1.5h, cooling to room temperature, and collecting nanoparticles to obtain the compound preparation;
(2) microwave synthesis of precursors Gd-OA and NaTFA-OA: 6mmol of Gd (CF) was taken3CO2)3·4H2Adding 25ml of oleic acid and 35ml of octadecene into a 100ml three-neck flask, then removing water and oxygen in vacuum, introducing pure argon for protection, and then heating to 125 ℃ for 45min by using a microwave synthesizer to react to obtain Gd-OA; take 40mmol of C2F3NaO2Putting (Na-TFA) and 50ml oleic acid into a single-mouth bottle, transferring into a microwave synthesizer, heating to 70 ℃ for 15min, and reacting for 40min to obtain Na-TFA-OA;
(3) microwave synthesis of NaYF by continuous layer-by-layer growth method4:5％Nd@NaGdF4: mixing 8.0mL of oleic acid and 12.0mL of octadecene, adding a cyclohexane solution containing 0.5mmol of NaYF4: 5% Nd, 10mL of Gd-OA and 2.5mL of a mixed precursor solution of Na-TFA-OA, removing cyclohexane in vacuum, introducing argon, transferring to a microwave synthesizer, and heating to 260 ℃ for 20min to react for 60min to obtain the compound preparation;
(4) microwave synthesis of NaYF by continuous layer-by-layer growth method4:5％Nd@NaGdF4@NaYbF 42% Er: mixing 5.0mL of oleic acid with 8.0mL of octadecene, and adding a mixture containing 0.25mmol of NaYF4:Nd@NaGdF4The preparation method comprises the following steps of (1) removing cyclohexane in vacuum, introducing argon, transferring to a microwave synthesizer, heating to 250 ℃ for 10min, and reacting for 60min to obtain the product, wherein the mixed precursor solution of Yb-OA, Er-OA and Na-TFA-OA is 6.25mL (the preparation methods of Yb-OA and Er-OA are the same as those of Gd-OA, and the volume ratio of Yb-OA, Er-OA and Na-TFA-OA is 3.92:0.08: 1);
(5) microwave synthesis of NaYF by continuous layer-by-layer growth method4:5％Nd@NaGdF4@NaYbF4：2％Er@NaYF4: mixing 5.0mL of oleic acid with 8.0mL of octadecene, and adding a mixture containing 0.25mmol of NaYF4:5％Nd@NaGdF4@NaYbF 42% Er in cyclohexane solution, 15mL Y-OA (prepared by the same method as Gd-OA)) And 3.75mL of mixed precursor solution of Na-TFA-OA, removing cyclohexane in vacuum, introducing argon, transferring to a microwave synthesizer, and heating to 260 ℃ for reaction for 60min after 10min to obtain the final product.
Example 3
An orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity is prepared by the following steps:
(1) microwave synthesis of NaYF 45% of Nd nanocrystalline: 0.95mmol of Y (CF)3CO2)3·4H2O、0.05mmol Nd(CF3CO2)3·4H2Mixing O, 15.0mL octadecene and 8.0mL oleic acid, removing water and oxygen in vacuum, introducing argon, transferring to a microwave synthesizer, heating to 125 deg.C for 20min, maintaining for 55min, cooling to 60 deg.C, adding a solution containing 2.5mmol NaOH and 4mmol NH4Reacting 6mL of methanol solution of F for 60min, introducing pure argon for protection, heating to 250 ℃ for 2h by using microwaves for 20min, cooling to room temperature, and collecting nanoparticles;
(2) microwave synthesis of precursors Gd-OA and NaTFA-OA: 6mmol of Gd (CF) was taken3CO2)3·4H2Adding 25ml of oleic acid and 35ml of octadecene into a 100ml three-neck flask, then removing water and oxygen in vacuum, introducing pure argon for protection, heating to 130 ℃ for reaction for 40min by using a microwave synthesizer for 15min, and obtaining Gd-OA; take 40mmol of C2F3NaO2Putting (Na-TFA) and 50ml oleic acid into a single-mouth bottle, transferring into a microwave synthesizer, heating to 65 ℃ for 20min, and reacting for 45min to obtain Na-TFA-OA;
(3) adopting a continuous layer-by-layer growth method to synthesize NaYF by microwave4:5％Nd@NaGdF4: mixing 4.0mL of oleic acid and 6.0mL of octadecene, adding a cyclohexane solution containing 0.25mmol of NaYF4: 5% Nd, 5mL of Gd-OA and 1.25mL of mixed precursor solution of Na-TFA-OA, removing cyclohexane in vacuum, introducing argon, transferring to a microwave synthesizer, heating to 260 ℃ for 15min, and reacting for 60min to obtain the nano-material;
(4) microwave synthesis of NaYF by continuous layer-by-layer growth method4:5％Nd@NaGdF4@NaYbF 42% Er: 5.0mL of oleic acid was mixed with 7.5mL of octadecene, and thenThen 0.25mmol NaYF is added4:Nd@NaGdF4The preparation method comprises the following steps of (1) removing cyclohexane in vacuum, introducing argon, transferring to a microwave synthesizer, heating to 260 ℃ for 15min, and reacting for 60min to obtain the product, wherein the mixed precursor solution of Yb-OA, Er-OA and Na-TFA-OA is 6.25mL (the preparation methods of Yb-OA and Er-OA are the same as those of Gd-OA, and the volume ratio of Yb-OA, Er-OA and Na-TFA-OA is 3.92:0.08: 1);
(5) microwave synthesis of NaYF by continuous layer-by-layer growth method4:5％Nd@NaGdF4@NaYbF4：2％Er@NaYF4: mixing 6.0mL of oleic acid with 9.0mL of octadecene, and adding a mixture containing 0.25mmol of NaYF4:5％Nd@NaGdF4@NaYbF4A mixed precursor solution of 2 percent Er cyclohexane solution, 20mL Y-OA (Gd-OA is used in the preparation method) and 5mL Na-TFA-OA, then cyclohexane is removed in vacuum, argon is introduced, the mixture is transferred to a microwave synthesizer, and the temperature is raised to 260 ℃ for reaction for 60min after 20min, thus obtaining the material.
From fig. 1, 4, 7, we can see: the nanoparticles exhibit a regular morphology.
From fig. 2 and 3, it can be seen that: the nano crystal nucleus finishes down-conversion under the excitation of 808nm to emit near-infrared 1050nm wavelength light, and the nano crystal nucleus excites NaYbF at 980nm4: the 2% Er shell layer completes up-conversion to emit 650nm wavelength light. From the emission spectrum, it is known that the nanoparticles exhibit excellent optical properties.
From fig. 5 and 6, it can be seen that: the nano crystal nucleus under the excitation of 808nm completes down-conversion to emit near-infrared 1050nm wavelength light, and the NaYbF is excited by 980nm4: the 2% Er shell layer completes up-conversion to emit 650nm wavelength light. As can be seen from the emission spectrum, the mass ratio of the core to the core shell under the excitation of 980nm wavelength light is 1: 2: 2: the 6 nanoparticles have the strongest excitation light of 650 nm.
From fig. 8, 9 it can be seen: the nano crystal nucleus finishes down-conversion under the excitation of 808nm to emit near-infrared 1050nm wavelength light, and the nano crystal nucleus excites NaYbF at 980nm4: the 2% Er shell layer completes up-conversion to emit 650nm wavelength light. As can be seen from the emission spectrum, the nanoparticles show excellent orthogonal fluorescence emission performance under the excitation of wavelength light of 808nm and 980 nm.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.

Claims (10)

1. A preparation method of orthogonal fluorescence emission rare earth core-shell nanocrystals with adjustable luminous intensity is characterized by comprising the following steps:
(1) synthesis of NaYF45% Nd nanocrystal core;
(2) microwave synthesis of precursors of rare earth element-OA and Na-TFA-OA: mixing trifluoroacetate, oleic acid and octadecene of rare earth elements, removing water and oxygen in vacuum, introducing protective gas, and performing microwave reaction at the temperature of 120-130 ℃ for 40-50min to obtain rare earth element-OA; c is to be2F3NaO2Mixing with oleic acid, and performing microwave reaction at 60-70 deg.C for 40-50min to obtain Na-TFA-OA;
(3) preparing the rare earth nanocrystalline with the core-shell structure by performing shell layer growth at least once by adopting a continuous layer-by-layer growth method: NaYF is added4Mixing a cyclohexane solution with 5 percent of Nd with oleic acid, octadecene, rare earth elements-OA and Na-TFA-OA, removing cyclohexane in vacuum, introducing protective gas, and carrying out microwave reaction at the temperature of 250 ℃ and 260 ℃ for 50-60min to obtain the Nd-Fe-B-O-doped barium niobate.
2. The method of claim 1, wherein NaYF is added to the reaction mixture4The synthesis of the 5 percent Nd nanocrystal comprises the following steps: mixing Y (CF)3CO2)3·4H2O、Nd(CF3CO2)3·4H2Mixing O, octadecene and oleic acid, removing water and oxygen in vacuum, introducing argon, reacting at the temperature of 120-130 ℃ for 40-60min, cooling to the temperature of 50-60 ℃, and adding NaOH and NH4Reacting the methanol solution of F for 50-60min, introducing nitrogen for protection, carrying out microwave reaction at 250-260 ℃ for 1-2h, and cooling to room temperature to obtain the catalyst.
3. The method of claim 2, wherein: the Y (CF)3CO2)3·4H2O、Nd(CF3CO2)3·4H2The dosage ratio of O, octadecene and oleic acid is 0.95-0.98 mol: 0.02-0.05 mol: 12-15L: 6 to 8L.
4. The method of claim 1, wherein: the dosage ratio of trifluoroacetate, oleic acid and octadecene of the rare earth elements is 6 mol: 24-26L: 34-36L.
5. The method of claim 1, wherein: said C is2F3NaO2And oleic acid in a ratio of 40 mol: 50L.
6. The method according to claim 1, wherein the rare earth element-OA is Gd-OA; the rare earth nanocrystalline with the core-shell structure is NaYF4:5％Nd@NaGdF4The preparation method comprises the following steps: forming a nuclear layer NaYF4Mixing a cyclohexane solution with 5 percent of Nd with oleic acid, octadecene, Gd-OA and Na-TFA-OA, removing cyclohexane in vacuum, introducing argon, and carrying out microwave reaction at the temperature of 250-260 ℃ for 50-60min to obtain the Nd-Fe-B-based catalyst.
7. The method according to claim 6, wherein the rare earth element-OA further comprises Yb-OA and Er-OA; the rare earth nanocrystalline with the core-shell structure is NaYF4:5％Nd@NaGdF4@NaYbF4The preparation method comprises the following steps: forming a core layer NaYF4:5％Nd@NaGdF4Mixing the cyclohexane solution with oleic acid, octadecene, Yb-OA, Er-OA and Na-TFA-OA, removing cyclohexane in vacuum, introducing argon, and carrying out microwave reaction at 250-260 ℃ for 50-60min to obtain the compound.
8. The method of claim 7, wherein the rare earth element-OA further comprises Y-OA; the rare earth nanocrystal with the core-shell structure is NaYF4:5％Nd@NaGdF4@NaYbF4:2％Er@NaYF4The preparation method comprises the following steps: forming a core layer NaYF4:5％Nd@NaGdF4@NaYbF4The cyclohexane solution is mixed with oleic acid, octadecene and Y-Mixing OA and Na-TFA-OA, removing cyclohexane in vacuum, introducing argon, and carrying out microwave reaction at 250-260 ℃ for 50-60min to obtain the product.
9. The method of claim 1, wherein: the NaYF4A5% Nd solution in cyclohexane was used in a ratio of 0.25mol of oleic acid, octadecene, rare earth elements-OA and Na-TFA-OA: 4-6L: 6-9L: 5-20L: 1.25-5L.
10. The orthogonal fluorescence emission rare earth core-shell nanocrystal with adjustable luminous intensity, prepared by the preparation method according to any one of claims 1 to 9.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865538A (en) * 2014-02-23 2014-06-18 复旦大学 Up/down conversion dual-mode fluorescent nanomaterial for Nd<3+> sensitization and synthesis method thereof
US20150362432A1 (en) * 2013-01-22 2015-12-17 University Of Massachusetts Medical School Compositions and methods for upconverting luminescence with engineered excitation and applications thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150362432A1 (en) * 2013-01-22 2015-12-17 University Of Massachusetts Medical School Compositions and methods for upconverting luminescence with engineered excitation and applications thereof
CN103865538A (en) * 2014-02-23 2014-06-18 复旦大学 Up/down conversion dual-mode fluorescent nanomaterial for Nd<3+> sensitization and synthesis method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘松彬 等，: ""上转换正交发光材料的纳米结构设计, 光色调控及应用"", 激光与光电子学进展, vol. 58, no. 15, pages 1 - 13 *

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