CN112794358A - Rare earth doped sodium yttrium fluoride core-shell structure nano material and preparation method thereof - Google Patents

Rare earth doped sodium yttrium fluoride core-shell structure nano material and preparation method thereof Download PDF

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CN112794358A
CN112794358A CN202110051428.9A CN202110051428A CN112794358A CN 112794358 A CN112794358 A CN 112794358A CN 202110051428 A CN202110051428 A CN 202110051428A CN 112794358 A CN112794358 A CN 112794358A
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rare earth
nayf
earth doped
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yttrium fluoride
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权泽卫
邓克荣
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Southwest University of Science and Technology
Southern University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • 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
    • C09K11/7704—Halogenides
    • C09K11/7705—Halogenides with alkali or alkaline earth metals
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • 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
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7772—Halogenides
    • C09K11/7773—Halogenides with alkali or alkaline earth metal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Abstract

The invention provides a rare earth doped sodium yttrium fluoride core-shell structure nano material, which has a chemical general formula as follows: NaY(1‑x)LnxF4@NaAF4Wherein Ln is one or more selected from Y, Ho, Er, Tm, Gd and La, and 0<x is less than or equal to 50mol percent, A is selected from one or more of Yb, Y, Ho, Er, Tm, Gd and La. The invention also provides a preparation method of the rare earth doped sodium yttrium fluoride core-shell structure nano material. The rare earth doped sodium yttrium fluoride core-shell structure nano material has good monodispersity, uniform size and appearance and high luminous efficiency, and shows potential application prospects in the fields of optical storage, illumination display, optical anti-counterfeiting, encoding and the like.

Description

Rare earth doped sodium yttrium fluoride core-shell structure nano material and preparation method thereof
Technical Field
The invention relates to the technical field of nano luminescent materials, in particular to a rare earth doped sodium yttrium fluoride core-shell structure nano material and a preparation method thereof.
Background
The rare earth doped up-conversion nanoparticles can convert near infrared light into visible light, and have the advantages of no background fluorescence, low toxicity, high light stability, deeper light penetration depth and the like, so that the rare earth doped up-conversion nanoparticles attract wide attention in various biological applications. The rare earth doped up-conversion nano material mainly comprises phosphate, vanadate, oxide, sulfide, fluoride and the like. The rare earth doped fluoride nano luminescent material has the characteristics of small phonon energy and high chemical stability, and has potential application value in the aspects of biological and medical detection. However, the up-conversion luminous efficiency of the existing rare earth doped sodium yttrium fluoride nano material is generally low, and the application of the nano material is limited.
Disclosure of Invention
The invention mainly aims to provide a rare earth doped sodium yttrium fluoride core-shell structure nano material, aiming at improving the up-conversion luminous efficiency of the rare earth doped sodium yttrium fluoride nano material.
In order to achieve the purpose, the invention provides a rare earth doped sodium yttrium fluoride core-shell structure nano material, which has a chemical general formula as follows: NaY(1-x)LnxF4@NaAF4Wherein Ln is one or more selected from Y, Ho, Er, Tm, Gd and La, and 0<x is less than or equal to 50mol percent, A is selected from one or more of Yb, Y, Ho, Er, Tm, Gd and La.
Optionally, the rare earth doped sodium yttrium fluoride core-shell structure nano material is of a hexagonal phase structure, and the size range is 5-100 nm.
Optionally, the rare earth-doped sodium yttrium fluoride core-shell structure nano material is oil-soluble nano particles, the rare earth-doped sodium yttrium fluoride core-shell structure nano material is a rare earth-doped sodium yttrium fluoride core-shell structure nano material, and the rare earth-doped sodium yttrium fluoride core-shell structure nano material is selected from any one or more of the following nano particles: NaYF4:5mol％Yb,0.5mol％Er@NaYF4Nanoparticles, NaYF4:20mol％Yb,2mol％Er@NaYF4Nanoparticles, NaYF4:18mol％,1mol％Tm@NaYF4Nanoparticles and NaYF4:20mol％Yb,1mol％Ho@NaYF4And (3) nanoparticles.
The invention also provides a preparation method of the rare earth doped sodium yttrium fluoride core-shell structure nano material, which comprises the following steps:
s1, preparing rare earth doped sodium yttrium fluoride nano material NaY(1-x)LnxF4The seed crystal is used as a core seed crystal, wherein Ln is selected from one or more of Y, Ho, Er, Tm, Gd and LaSeed, 0<x≤50mol％；
S2, preparing a metal salt solution as a shell precursor solution, wherein the metal in the metal salt solution is selected from one or more of Na, Y, Yb, Ho, Er, Tm, Gd and La;
s3, adding the kernel seed crystal obtained in the step S1 into the shell precursor solution obtained in the step S2;
s4, adding a methanol solution of ammonium fluoride into the mixed solution obtained in the step S3, and reacting to obtain the rare earth doped sodium yttrium fluoride core-shell structure nano material; and the number of the first and second groups,
s5, taking the rare earth doped sodium yttrium fluoride core-shell structure nano material as an inner core seed crystal, and repeating the steps S2-S4 to obtain the rare earth doped sodium yttrium fluoride multi-shell layer core-shell structure nano material.
Further, in step S2, the metal salt solution is any one of a halide solution, an acetate solution and a nitrate solution, wherein the acetate solution is selected from one or more of a sodium acetate solution, a yttrium acetate solution, an ytterbium acetate solution, an erbium acetate solution, a holmium acetate solution, a thulium acetate solution, a gadolinium acetate solution and a lanthanum acetate solution.
Further, the step S2 specifically includes the following steps:
s21, dissolving a metal salt in a mixed solvent of oleic acid and octadecene to obtain a metal salt mixed solution, wherein the volume ratio of oleic acid to octadecene is 1-10: 1-100; and the number of the first and second groups,
and S22, under the protection of inert gas, heating the metal salt mixed solution obtained in the step S21 to 100-160 ℃, preserving heat for 0.5-1 h, and then cooling to 5-50 ℃ to obtain a clarified metal salt solution.
Further, in the step S3, the molar ratio of the core seed crystal to the shell precursor is 4: 1-1: 5.
Further, in the step S4, the molar amount of ammonium fluoride in the methanol solution of ammonium fluoride is 4 to 4.2 times of the molar amount of the metal salt in the metal salt solution.
Further, in the step S4, the reaction temperature is 280 to 350 ℃, and the reaction time is 5 to 180 min.
According to the technical scheme, the rare earth doped sodium yttrium fluoride nano material is used as the inner core for epitaxial growth, and the core-shell structure nano material with uniform coating is obtained. According to the spectrum test result, the luminous efficiency of the coated nano material is greatly improved, and the fluorescence quantum yield is correspondingly improved. In addition, the nano material has good monodispersity, uniform size and appearance and high luminous efficiency, and shows potential application prospects in the fields of optical storage, illumination display, optical anti-counterfeiting, encoding and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
NaYF obtained in figure 1, comparative example 1 and example 145 mol% Yb,0.5 mol% Er nanoparticles and NaYF4:5mol％Yb,0.5mol％Er@NaYF4Powder diffraction pattern of nanoparticles.
FIG. 2, (a) NaYF obtained in comparative example 1420 mol% Yb,2 mol% Er nanoparticles, (b) NaYF obtained in example 14:20mol％Yb,2mol％Er@NaYF4Transmission electron microscopy of nanoparticles.
NaYF obtained in FIG. 3, comparative example 1 and example 145 mol% Yb,0.5 mol% Er nanoparticles and NaYF4:5mol％Yb,0.5mol％Er@NaYF4The upconversion emission spectrum of the nanoparticles (excitation 980 nm).
NaYF obtained in FIG. 4, comparative example 2 and example 2420 mol% Yb,2 mol% Er nanoparticles and NaYF4:20mol％Yb,2mol％Er@NaYF4Powder diffraction pattern of nanoparticles.
NaYF obtained in FIG. 5, comparative example 2 and example 2420 mol% Yb,2 mol% Er nanoparticles and NaYF4:20mol％Yb,2mol％Er@NaYF4Up-conversion of nanoparticlesEmission spectrum (excitation 980 nm).
NaYF obtained in FIG. 6, example 1 and example 24:5mol％Yb,0.5mol％Er@NaYF4Nanoparticles and NaYF4:20mol％Yb,2mol％Er@NaYF4Upconversion emission spectrum (excitation 980 nm).
NaYF obtained in FIG. 7, comparative example 3 and example 3418 mol%, 1 mol% Tm nanoparticles and NaYF4:18mol％,1mol％Tm@NaYF4Powder diffraction pattern of nanoparticles.
FIG. 8, (a) NaYF obtained in comparative example 3418 mol%, 1 mol% Tm nanoparticles, (b) 18 mol%, 1 mol% Tm @ NaYF, NaYF4 obtained in example 34Transmission electron microscopy of nanoparticles.
NaYF obtained in FIG. 9, comparative example 4 and example 4420 mol% Yb,1 mol% Ho nanoparticles and NaYF4:20mol％Yb,1mol％Ho@NaYF4Powder diffraction pattern of nanoparticles.
FIG. 10, (a) NaYF of comparative examples 4 to 4420 mol% Yb,1 mol% Ho nanoparticles, (b) NaYF obtained in example 44:20mol％Yb,1mol％Ho@NaYF4Transmission electron microscopy of nanoparticle images.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
If there is a description of "first", "second", etc. in an embodiment of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, the meaning of "and/or" appearing throughout is to include three juxtapositions, exemplified by "A and/or B," including either the A or B arrangement, or both A and B satisfied arrangement. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The embodiment of the invention provides a rare earth doped sodium yttrium fluoride core-shell structure nano material, which has a chemical general formula as follows: NaY(1-x)LnxF4@NaAF4Wherein Ln is one or more selected from Y, Ho, Er, Tm, Gd and La, and 0<x is less than or equal to 50mol percent, A is selected from one or more of Yb, Y, Ho, Er, Tm, Gd and La.
In some embodiments of the invention, an improved high-temperature coprecipitation method is adopted to synthesize a rare earth doped sodium yttrium fluoride nano material, the rare earth doped sodium yttrium fluoride nano material is used as an inner core for epitaxial growth to prepare a uniformly coated rare earth doped sodium yttrium fluoride core-shell structure nano material, and the rare earth doped sodium yttrium fluoride multi-shell core-shell structure nano material is prepared after further coating.
According to the embodiment of the invention, the rare earth doped sodium yttrium fluoride nanometer material, the rare earth doped sodium yttrium fluoride core-shell structure nanometer material and the rare earth doped sodium yttrium fluoride multi-shell layer core-shell structure nanometer material are in hexagonal phase structures, are uniform in size and appearance, and have the size range of 5-100 nm.
According to the embodiment of the invention, the rare earth doped sodium yttrium fluoride nano material, the rare earth doped sodium yttrium fluoride core-shell structure nano material and the rare earth doped sodium yttrium fluoride multi-shell layer core-shell structure nano material are oil-soluble nano particles.
According to the embodiment of the invention, the rare earth doped sodium yttrium fluoride nano material used as the inner core can be selected from one or more of the following nanoparticles: NaYF4:5mol％Yb,0.5mol％Er nanoparticles, NaYF 420 mol% of Yb,2 mol% of Er nano particles and NaYF418 mol%, 1 mol% Tm nanoparticles and NaYF 420 mol% Yb,1 mol% Ho nanoparticles.
The rare earth doped sodium yttrium fluoride core-shell structure nano material is selected from any one or more of the following nano particles: NaYF4:5mol％Yb,0.5mol％Er@NaYF4Nanoparticles, NaYF4:20mol％Yb,2mol％Er@NaYF4Nanoparticles, NaYF4:18mol％,1mol％Tm@NaYF4Nanoparticles and NaYF4:20mol％Yb,1mol％Ho@NaYF4And (3) nanoparticles.
The embodiment of the invention also provides a preparation method of the rare earth doped sodium yttrium fluoride core-shell structure nano material, which comprises the following steps:
s1, preparing rare earth doped sodium yttrium fluoride nano material NaY(1-x)LnxF4The seed crystal is used as a core seed crystal, wherein Ln is selected from one or more of Y, Ho, Er, Tm, Gd and La, and 0<x≤50mol％；
S2, preparing a metal salt solution as a shell precursor solution, wherein the metal in the metal salt solution is selected from one or more of Na, Y, Yb, Ho, Er, Tm, Gd and La;
s3, adding the kernel seed crystal obtained in the step S1 into the shell precursor solution obtained in the step S2;
and S4, adding a methanol solution of ammonium fluoride into the mixed solution obtained in the step S3, and reacting to obtain the rare earth doped sodium yttrium fluoride core-shell structure nano material.
Further, the step S1 specifically includes the following steps:
s11, preparing a metal salt solution, wherein the metal in the metal salt solution is selected from one or more of Na, Y, Yb, Ho, Er, Tm, Gd and La;
s12, adding a methanol solution of ammonium fluoride into the solution obtained in the step S11, and reacting to obtain the rare earth doped sodium yttrium fluoride nano material NaY(1-x)LnxF4；
Wherein the metal salt solution can be halide solution, acetate solution or nitrate solutionPreferably, a halide solution or an acetate solution, and more preferably an acetate solution. Wherein the acetate solution is selected from one or more of sodium acetate, yttrium acetate, ytterbium acetate, erbium acetate, holmium acetate, thulium acetate, gadolinium acetate and lanthanum acetate. The dosage of the metal salt in the metal salt solution conforms to NaY(1-x)LnxF4Wherein x and Ln have the same meanings as defined above.
According to the embodiment of the present invention, the step S11 specifically includes: dissolving a metal salt in a solvent R at 5-50 ℃ (such as room temperature), heating to 100 ℃ and 160 ℃ under the protection of inert gas, preserving the temperature for 30min, and then cooling to 5-50 ℃ (such as room temperature) to obtain a clear solution. Wherein, the solvent R is selected from a mixed solution of oleic acid (or oleylamine) and octadecene, the volume ratio of the oleic acid to the octadecene is 1-10: 1-100, preferably 2-6: 2-50, and for example, the mixed solution of oleic acid and octadecene with the volume ratio of 2:3 is used as the solvent.
According to an embodiment of the present invention, in the step S12, the molar amount of ammonium fluoride in the methanol solution of ammonium fluoride may be 4 times the molar amount of sodium salt in the metal sodium salt solution used in the step S11.
According to an embodiment of the present invention, in the step S12, the reaction temperature is 280-350 ℃, and the reaction time is 5-180 min.
In step S2, the metal salt solution is any one of halide solution, acetate solution and nitrate solution, wherein the acetate solution is selected from one or more of sodium acetate solution, yttrium acetate solution, ytterbium acetate solution, erbium acetate solution, holmium acetate solution, thulium acetate solution, gadolinium acetate solution and lanthanum acetate solution.
The step S2 specifically includes the following steps:
s21, dissolving a metal salt in a mixed solvent of oleic acid (or oleylamine) and octadecene to obtain a metal salt mixed solution; and the number of the first and second groups,
and S22, under the protection of inert gas, heating the metal salt mixed solution obtained in the step S21 to 100-160 ℃, preserving the heat for 30-XXmin, and then cooling to 5-50 ℃ to obtain a clarified metal salt solution.
In the step S21, the volume ratio of oleic acid (or oleylamine) to octadecene is 1-10: 1-100, preferably 2-6: 2-50.
In the step S3, the molar ratio of the kernel seed crystal to the shell precursor is 4: 1-1: 5.
In the step S4, the molar weight of ammonium fluoride in the methanol solution of ammonium fluoride is 4 to 4.2 times of the molar weight of the metal salt in the metal salt solution.
In the step S4, the reaction temperature is 280-350 ℃, and the reaction time is 5-180 min.
Also, in the step S51, the metal salt solution is any one of a halide solution, an acetate solution and a nitrate solution, wherein the acetate solution is selected from one or more of a sodium acetate solution, a yttrium acetate solution, an ytterbium acetate solution, an erbium acetate solution, a holmium acetate solution, a thulium acetate solution, a gadolinium acetate solution and a lanthanum acetate solution.
The step S52 specifically includes the following steps:
s521, dissolving a metal salt in a mixed solvent of oleic acid (or oleylamine) and octadecene to obtain a metal salt mixed solution; and the number of the first and second groups,
and S522, under the protection of inert gas, heating the metal salt mixed solution obtained in the step S21 to 100-160 ℃, preserving heat for 0.5-1 h, and then cooling to 5-50 ℃ to obtain a clarified metal salt solution.
In the step S521, the volume ratio of oleic acid (or oleylamine) to octadecene is 1-10: 1-100, preferably 2-6: 2-50.
In the step S53, the molar ratio of the kernel seed crystal to the shell precursor is 4: 1-1: 5.
In the step S54, the molar weight of ammonium fluoride in the methanol solution of ammonium fluoride is 4 to 4.2 times of the molar weight of the metal salt in the metal salt solution.
In the step S55, the reaction temperature is 280-350 ℃, and the reaction time is 5-180 min.
The following will combine specific examples and comparative examples to further illustrate the rare earth doped sodium yttrium fluoride core-shell structured nanomaterial of the present invention. It is to be understood that the following description is only exemplary, and not restrictive of the invention.
Unless otherwise indicated, the starting materials and reagents used in the examples are all commercially available materials or prepared by known methods.
Comparative example 1: NaYF45mol percent of Yb and 0.5mol percent of Er nano-particles. 0.005mmol of Er (CH) was weighed3COO)3·4H2O、0.05mmol Yb(CH3COO)3·4H2O and 0.945mmol Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution A, and then cooling to room temperature; 2.25mmol NaOH and 4mmol NH were weighed4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution A, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution B; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF45 mol% of Yb and 0.5 mol% of Er nano-particles.
Example 1: NaYF4:5mol％Yb,0.5mol％Er@NaYF4And (4) preparing nanoparticles. 0.005mmol of Er (CH) was weighed3COO)3·4H2O、0.05mmol Yb(CH3COO)3·4H2O and 0.945mmol Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution A, and then cooling to room temperature; NaOH and 4mmol of NH were weighed4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution A, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution B; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF45 mol% of Yb and 0.5 mol% of Er nano-particles. Mixing oil soluble NaYF45mol percent of Yb and 0.5mol percent of Er nano particles are taken as kernel seed crystals to carry out core-shell coating. Weighing 1mmol of Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃ and keepingWarming for 30 minutes to form a clear solution C, adding 1mmol NaYF4:5mol％Yb,0.5mol％Er@NaYF4And (4) carrying out kernel seed crystal. Stirring for 10min, weighing 2.25mmol NaOH and 4mmol NH4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution C, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution D; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF4:5mol％Yb,0.5mol％Er@NaYF4And (3) nanoparticles.
Comparative example 2: NaYF420mol percent of Yb and 2mol percent of Er nano-particles. 0.02mmol of Er (CH) was weighed3COO)3·4H2O、0.2mmolYb(CH3COO)3·4H2O and 0.78mmol Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution A, and then cooling to room temperature; 2.25mmol NaOH and 4mmol NH were weighed4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution A, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution B; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF 420 mol% of Yb and 2 mol% of Er nano-particles.
Example 2: NaYF4:20mol％Yb,2mol％Er@NaYF4And (4) preparing nanoparticles. 0.02mmol of Er (CH) was weighed3COO)3·4H2O、0.2mmol Yb(CH3COO)3·4H2O and 0.78mmol Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution A, and then cooling to room temperature; 2.25mol NaOH and 4mmol NH were weighed4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution A, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution B; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF 420 mol% of Yb and 2 mol% of Er nano-particles. Mixing oil soluble NaYF420mol percent of Yb and 2mol percent of Er nano particles are taken as kernel seed crystals to carry out core-shell coating. Weighing 1mmol of Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution C, and adding 1mmol of NaYF 420 mol% Yb and 2 mol% Er core seed crystal. Stirring for 10min, weighing 2.25mmol NaOH and 4mmol NH4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution C, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution D; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF4:20mol％Yb,2mol％Er@NaYF4And (3) nanoparticles.
Comparative example 3: NaYF418 mol%, 1 mol% Tm nanoparticles. Weighing 0.01mmol Tm (CH)3COO)3·4H2O、0.18mmolYb(CH3COO)3·4H2O and 0.81mmol Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution A, and then cooling to room temperature; 2.25mmol NaOH and 4mmol NH were weighed4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution A, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution B; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF418 mol% Yb,1 mol% Tm nanoparticles.
Example 3: NaYF4:18mol％,1mol％Tm@NaYF4And (4) preparing nanoparticles. Weighing 0.01mmol Tm (CH)3COO)3·4H2O、0.18mmol Yb(CH3COO)3·4H2O and 0.79mmol Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution A, and then cooling to room temperature; 2.25mol NaOH and 4mmol NH were weighed4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution A, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution B; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF418 mol%, 1 mol% Tm nanoparticles. Mixing oil soluble NaYF418mol percent of Tm nano particles and 1mol percent of Tm nano particles are taken as kernel seed crystals to carry out core-shell coating. Weighing 1mmol of Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution C, and adding 1mmol of NaYF418 mol%, 1 mol% Tm core seed crystal. Stirring for 10min, weighing 2.25mmol NaOH and 4mmol NH4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution C, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution D; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF4:18mol％,1mol％Tm@NaYF4And (3) nanoparticles.
Comparative example 4: NaYF4Preparation of 20 mol% Yb,1 mol% Ho nanoparticles. 0.01mmol of Ho (CH) was weighed3COO)3·4H2O、0.2mmolYb(CH3COO)3·4H2O and 0.79mmol Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution A, and then cooling to room temperature; 2.25mmol NaOH and 4mmol NH were weighed4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution A, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution B; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for several times; adding 20mL of ethanol for precipitation separation and washing for several times to obtain the oil-soluble NaYF 420 mol% Yb,1 mol% Ho nanoparticles.
Example 4: NaYF4:20mol％Yb,1mol％Ho@NaYF4And (4) preparing nanoparticles. 0.01mmol of Ho (CH) was weighed3COO)3·4H2O、0.2mmolYb(CH3COO)3·4H2O and 0.79mmol Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution A, and then cooling to room temperature; 2.25mmol NaOH and 4mmol NH were weighed4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution A, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution B; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF 420 mol% Yb,1 mol% Ho nanoparticles. Mixing oil soluble NaYF420mol percent of Yb and 1mol percent of Ho nano particles are taken as kernel seed crystals to carry out core-shell coating. Weighing 1mmol of Y (CH)3COO)3·4H2O, then adding 8mL of oleic acid and 12mL of octadecene, introducing nitrogen, heating to 120 ℃, preserving heat for 30 minutes to form a transparent solution C, and adding 1mmol of NaYF 420 mol% Yb,1 mol% Ho core seed crystal. Stirring for 10min, weighing 2.25mmol NaOH and 4mmol NH4Dissolving the mixture in 10mL of methanol, dropwise adding the mixture into the solution C, continuously stirring for 10min to fully mix the mixture, heating to 60 ℃, and preserving the temperature for 30min to form a transparent solution D; heating to 280 ℃, preserving heat for 1h, and cooling to room temperature; adding 20mL of ethanol for precipitation separation and washing for a plurality of times to obtain the oil-soluble NaYF4:20mol％Yb,1mol％Ho@NaYF4And (3) nanoparticles.
The testing process comprises the following steps: the products obtained in the above examples and comparative examples were characterized by powder diffraction using a SmartLab apparatus manufactured by Nippon Kogyo Co., Ltd. (Rigaku) and a copper target radiation wavelength of λ 0.154187 nm.
The products obtained in the above examples and comparative examples were examined by transmission electron microscopy using an instrument type HT7700, manufactured by Hitachi (Hitachi).
The products obtained in the above examples and comparative examples were characterized by their upconversion emission spectra (excitation 980nm) using a Scientific FluoroMax-4 instrument manufactured by HORIBA (HORIBA).
As shown in FIG. 1, from the comparative exampleThe powder diffraction patterns of the products obtained from example 1 and example 1 respectively can be seen, NaYF45 mol% Yb,0.5 mol% Er nanoparticles and NaYF4:5mol％Yb,0.5mol％Er@NaYF4Nanoparticles have all been successfully synthesized.
As shown in FIG. 2, from the transmission electron micrographs of the products obtained in comparative example 1 and example 1, respectively, NaYF can be seen4:5mol％Yb,0.5mol％Er@NaYF4The size of the nano particles is obviously larger than NaYF45 mol% Yb,0.5 mol% Er nanoparticles due to the size of the NaYF4:5mol％Yb,0.5mol％Er@NaYF4The nanoparticles are made of NaYF45 mol% Yb and 0.5 mol% Er nano particles are taken as kernel seed crystals and then coated with a layer of shell, which also indicates that the rare earth doped sodium yttrium fluoride core-shell structure nano material with uniform coating can be prepared by epitaxial growth on the basis of taking the rare earth doped sodium yttrium fluoride nano material as the kernel.
As shown in FIG. 3, NaYF can be seen from the up-conversion emission spectra of the products obtained in comparative example 1 and example 1, respectively4:5mol％Yb,0.5mol％Er@NaYF4The up-conversion luminous efficiency of the nano particles is obviously higher than that of NaYF4Compared with the uncoated rare earth doped sodium yttrium fluoride nano material, the coated rare earth doped sodium yttrium fluoride core-shell structure nano material has the advantage that the luminous efficiency can be greatly improved.
As shown in FIG. 4, NaYF can be seen from the powder diffraction patterns of the products obtained in comparative example 2 and example 2, respectively420 mol% Yb,2 mol% Er nanoparticles and NaYF4:20mol％Yb,2mol％Er@NaYF4Nanoparticles have all been successfully synthesized.
As shown in FIG. 5, NaYF can be seen from the up-conversion emission spectra of the products obtained in comparative example 2 and example 2, respectively4:20mol％Yb,2mol％Er@NaYF4The up-conversion luminous efficiency of the nano particles is obviously higher than that of NaYF 420 mol% Yb and 2 mol% Er nano particles, which shows that compared with the uncoated rare earth doped sodium yttrium fluoride nano material, the luminous efficiency of the coated rare earth doped sodium yttrium fluoride core-shell structure nano material can be greatly improved.
As shown in FIG. 6, NaYF can be seen from the up-conversion emission spectra of the products obtained in example 1 and example 2, respectively4:20mol％Yb,2mol％Er@NaYF4The up-conversion luminous efficiency of the nano particles is obviously higher than that of NaYF4:5mol％Yb,0.5mol％Er@NaYF4And the nano particles show that in the rare earth doped sodium yttrium fluoride core-shell structure nano material, the higher the doping proportion of the rare earth element is, the higher the up-conversion luminous efficiency is.
As shown in FIG. 7, NaYF can be seen from the powder diffraction patterns of the products obtained in comparative example 3 and example 3, respectively418 mol%, 1 mol% Tm nanoparticles and NaYF4:18mol％,1mol％Tm@NaYF4Nanoparticles have all been successfully synthesized.
As shown in FIG. 8, from the transmission electron micrographs of the products obtained in comparative example 3 and example 3, respectively, NaYF4:18 mol%, 1 mol% Tm @ NaYF4The size of the nano particles is obviously larger than NaYF418 mol%, 1 mol% Tm nanoparticles size due to NaYF4:18 mol%, 1 mol% Tm @ NaYF4The nanoparticles are made of NaYF418mol percent of Tm nano particles with the concentration of 1mol percent are taken as seed crystals of a core and then coated with a layer of shell, which also indicates that the rare earth doped sodium yttrium fluoride nano material with uniform coating can be prepared by epitaxial growth on the basis of taking the rare earth doped sodium yttrium fluoride nano material as the core.
As shown in FIG. 9, NaYF can be seen from the powder diffraction patterns of the products obtained in comparative example 4 and example 4, respectively420 mol% Yb,1 mol% Ho nanoparticles and NaYF4:20mol％Yb,1mol％Ho@NaYF4Nanoparticles have all been successfully synthesized.
As shown in FIG. 10, from the transmission electron micrographs of the products obtained in comparative example 3 and example 3, respectively, NaYF can be seen4:20mol％Yb,1mol％Ho@NaYF4The size of the nano particles is obviously larger than NaYF 420 mol% Yb,1 mol% Ho nanoparticles size, due to NaYF4:20mol％Yb,1mol％Ho@NaYF4The nanoparticles are made of NaYF 420 mol% Yb and 1 mol% Ho nano-particles are used as seed crystals of a kernel and then coated with a shell layer to formThe fact that the rare earth doped sodium yttrium fluoride core-shell structure nano material with uniform coating can be prepared by epitaxial growth on the basis of taking the rare earth doped sodium yttrium fluoride nano material as the core is also demonstrated.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (9)

1. A rare earth doped sodium yttrium fluoride core-shell structure nano material is characterized in that the chemical general formula is as follows: NaY(1-x)LnxF4@NaAF4Wherein Ln is one or more selected from Y, Ho, Er, Tm, Gd and La, and 0<x is less than or equal to 50mol percent, A is selected from one or more of Yb, Y, Ho, Er, Tm, Gd and La.
2. The rare earth doped sodium yttrium fluoride core-shell structure nanomaterial of claim 1, wherein the rare earth doped sodium yttrium fluoride core-shell structure nanomaterial is in a hexagonal phase structure, and the particle diameter range is 5-100 nm.
3. The rare earth doped sodium yttrium fluoride core-shell structured nanomaterial of claim 2, wherein the rare earth doped sodium yttrium fluoride core-shell structured nanomaterial is an oil soluble nanoparticle, the rare earth doped sodium yttrium fluoride core-shell structured nanomaterial is a rare earth doped sodium yttrium fluoride core-shell structured nanomaterial, and the rare earth doped sodium yttrium fluoride core-shell structured nanomaterial is selected from any one or more of the following nanoparticles: NaYF4:5mol％Yb,0.5mol％Er@NaYF4Nanoparticles, NaYF4:20mol％Yb,2mol％Er@NaYF4Nanoparticles, NaYF4:18mol％,1mol％Tm@NaYF4Nanoparticles and NaYF4:20mol％Yb,1mol％Ho@NaYF4And (3) nanoparticles.
4. A preparation method of a rare earth doped sodium yttrium fluoride core-shell structure nano material is characterized by comprising the following steps:
s1, preparing rare earth doped sodium yttrium fluoride nano material NaY(1-x)LnxF4The seed crystal is used as a core seed crystal, wherein Ln is selected from one or more of Y, Ho, Er, Tm, Gd and La, and 0<x≤50mol％；
S2, preparing a metal salt solution as a shell precursor solution, wherein the metal in the metal salt solution is selected from one or more of Na, Y, Yb, Ho, Er, Tm, Gd and La;
s3, adding the kernel seed crystal obtained in the step S1 into the shell precursor solution obtained in the step S2;
and S4, adding a methanol solution of ammonium fluoride into the mixed solution obtained in the step S3, and reacting to obtain the rare earth doped sodium yttrium fluoride core-shell structure nano material.
5. The method for preparing a rare earth doped sodium yttrium fluoride core-shell structured nanomaterial as claimed in claim 4, wherein in the step S2, the metal salt solution is any one of a halide solution, an acetate solution and a nitrate solution, wherein the acetate solution is selected from one or more of a sodium acetate solution, a yttrium acetate solution, an ytterbium acetate solution, an erbium acetate solution, a holmium acetate solution, a thulium acetate solution, a gadolinium acetate solution and a lanthanum acetate solution.
6. The method for preparing a rare earth doped sodium yttrium fluoride core-shell structure nanomaterial as claimed in claim 4, wherein the step S2 specifically comprises the following steps:
s21, dissolving a metal salt in a mixed solvent of oleic acid and octadecene to obtain a metal salt mixed solution, wherein the volume ratio of oleic acid to octadecene is 1-10: 1-100; and the number of the first and second groups,
and S22, under the protection of inert gas, heating the metal salt mixed solution obtained in the step S21 to 100-160 ℃, preserving heat for 0.5-1 h, and then cooling to 5-50 ℃ to obtain a clarified metal salt solution.
7. The preparation method of the rare earth doped sodium yttrium fluoride core-shell structure nanomaterial as claimed in claim 4, wherein in the step S3, the molar ratio of the core seed crystal to the shell precursor is 4: 1-1: 5.
8. The method for preparing a rare earth doped sodium yttrium fluoride core-shell structured nanomaterial according to claim 4, wherein in the step S4, the molar amount of ammonium fluoride in the methanol solution of ammonium fluoride is 4-4.2 times of the molar amount of metal salt in the metal salt solution.
9. The method for preparing a rare earth doped sodium yttrium fluoride core-shell structure nanomaterial according to claim 4, wherein in the step S4, the reaction temperature is 280-350 ℃ and the reaction time is 5-180 min.
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