CN113292988A - Rare earth core-shell nano material and preparation method thereof - Google Patents

Rare earth core-shell nano material and preparation method thereof Download PDF

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CN113292988A
CN113292988A CN202110582514.2A CN202110582514A CN113292988A CN 113292988 A CN113292988 A CN 113292988A CN 202110582514 A CN202110582514 A CN 202110582514A CN 113292988 A CN113292988 A CN 113292988A
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rare earth
solution
nano material
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郑海荣
盛宗海
胡德红
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Shenzhen Institute of Advanced Technology of CAS
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    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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Abstract

The application provides a preparation method of a rare earth core-shell nano material, which comprises the following steps: carrying out first mixing treatment on a terbium salt, a lutetium salt, a base and a solvent to form a first solution; carrying out second mixing treatment on the first solution and ammonium fluoride to obtain a second solution; placing the second solution in a hydrothermal kettle for reaction to obtain a rare earth core nano material; the rare earth core nano material comprises a molecular formula of NaLuF4Nanoparticles of Tb; carrying out third mixing treatment on yttrium salt, a rare earth core nano material, alkali and a solvent to form a third solution; carrying out fourth mixing treatment on the third solution and ammonium fluoride to obtain a fourth solution; placing the fourth solution in a hydrothermal kettle for reaction to obtain the rare earth core-shell nano material, wherein the rare earth core-shell nano material comprises a molecular formula of NaYF4Shell of. The method prepares the rare earth luminescent nano material by using a water phase system, the process is simple, the obtained rare earth core-shell nano material has regular appearance and can generate stronger luminescent effect under the excitation of X rays, and the method is favorable for applying the rare earth core-shell nano material in biological imaging.

Description

Rare earth core-shell nano material and preparation method thereof
Technical Field
The application relates to the field of nano materials, in particular to a rare earth core-shell nano material and a preparation method thereof.
Background
Rare earth luminescent nanomaterials are a class of photoluminescent materials that store excitation energy in the material and release the stored energy as radiant luminescence after the excitation light ceases to illuminate. The rare earth luminescent nano material has the advantages of narrow emission, long service life, photobleaching resistance and the like, and has important application value in the aspects of biological marking and biological imaging.
The exciting light of the rare earth luminescent nano material used for biological imaging at present is an infrared band, but the infrared light has the defects of poor tissue penetrability, poor stereospecificity and the like, so that the rare earth luminescent nano material has low luminous efficiency and poor imaging effect. The X-ray has good penetrability to a human body, and is beneficial to being applied to biological imaging, however, the rare earth luminescent nano material for realizing biological imaging by taking the X-ray as exciting light has fewer varieties, the preparation method is complex, the production cost is high, the synthesis time is long, and the obtained rare earth luminescent nano material has poor stability and is not beneficial to popularization and application.
Disclosure of Invention
In view of the above, the present application provides a rare earth core-shell nanomaterial and a preparation method thereof, the method adopts a water phase system to prepare the rare earth luminescent nanomaterial, the stability of the rare earth luminescent nanomaterial is improved, the preparation process is simple, the cost is low, and the method is beneficial to large-scale production, and the obtained rare earth core-shell nanomaterial is not only regular in morphology and uniform in particle size, but also can generate a strong luminescent effect under the excitation of X-rays, and is beneficial to the application of the rare earth core-shell nanomaterial in biological imaging. The application also provides a rare earth core-shell nano material which has good stability and higher luminous efficiency and can be applied to the fields of biological marking, biological imaging and the like.
The first aspect of the application provides a preparation method of a rare earth core-shell nano material, which comprises the following steps:
carrying out first mixing treatment on a terbium salt, a lutetium salt, a base and a solvent to form a first solution; the solvent comprises water, n-butanol and oleic acid in a volume ratio of 1 (0.1-10) to (0.1-10);
carrying out second mixing treatment on the first solution and ammonium fluoride to obtain a second solution; placing the second solution in a hydrothermal kettle, and reacting at 100-300 ℃ for 1-72 h to obtain the rare earth core nano material; the rare earth core nano material comprises beta-NaLuF4:Tb；
Carrying out third mixing treatment on yttrium salt, the rare earth core nano material, the alkali and the solvent to form a third solution;
carrying out fourth mixing treatment on the third solution and ammonium fluoride to obtain a fourth solution; putting the fourth solution into a hydrothermal kettle, and reacting for 1-72 h at 100-300 ℃ to obtain the rare earth core-shell nano material, wherein the shell layer of the rare earth core-shell nano material comprises NaYF4。
The molecular formula of beta-NaLuF is prepared by adopting a water phase synthesis method4:Tb@NaYF4Rare earth core-shell nanomaterial, wherein, beta-NaLuF4Tb is the core body of rare-earth core-shell nano material, NaYF4Is a shell of rare earth core-shell nano material. In the aqueous phase synthesis method, n-butyl alcohol and oleic acid in a solvent can form microemulsion with water, so that metal ions in the solution are adsorbed, the reaction is carried out in microbubbles of the microemulsion, the structural uniformity of the rare earth nano material is improved, and the rare earth core-shell nano material has narrower particle size distribution and dispersion performance; and the obtained rare earth core-shell nano material has high crystalline phase purity and stable luminescence property, and is beneficial to being applied to biological imaging.
Optionally, the terbium salt includes one or more of terbium chloride, terbium acetate and terbium nitrate.
Optionally, the lutetium salt includes one or more of lutetium chloride, lutetium nitrate, and lutetium acetate.
Optionally, the molar ratio of the terbium salt to the lutetium salt in the first solution is 1 (4-99).
Optionally, the sum of the molar concentrations of the terbium salt and the lutetium salt in the first solution c1Is 0.1 mol. L-1-2mol·L-1。
Optionally, the sum of the molar concentrations of the terbium salt and the lutetium salt in the second solution c1With the molar concentration c of the ammonium fluorideF1The ratio of the components is 1 (1-50).
Optionally, the base comprises one or more of sodium hydroxide and potassium hydroxide.
Optionally, the volume ratio of n-butanol to oleic acid is 1 (0.1-10).
Optionally, the molar concentration of yttrium salt in the third solution is 0.1mol · L-1-2mol·L-1。
Optionally, in the third solution, the molar ratio of the yttrium salt to the rare earth core nanomaterial is 1 (10-100).
Optionally, the molar concentration ratio of the yttrium salt to the ammonium fluoride in the fourth solution is 1 (1-50).
Optionally, the pH of the first solution and the third solution is 10-12.
Optionally, the first mixing treatment, the second mixing treatment, the third mixing treatment and the fourth mixing treatment are mixed by using probe ultrasound, and the power of the probe ultrasound is 50W-500W.
Optionally, the temperature of the first mixing treatment, the second mixing treatment, the third mixing treatment and the fourth mixing treatment is 0 ℃ to 10 ℃.
The application synthesizes highly uniform and monodisperse beta-NaLuF through a water phase synthesis method4:Tb@NaYF4The preparation method of the rare earth core-shell nano material has the advantages of simple steps, easily controlled reaction conditions and low production cost, and the prepared rare earth core-shell nano material has bright afterglow, long afterglow time, stable chemical properties, no radioactivity and higher safety to human bodies.
The second aspect of the application provides a rare earth core-shell nano material, wherein the rare earth core-shell nano material comprises a rare earth core nano material and a shell layer coated on the surface of the rare earth core nano material; the rare earth core nano material comprises beta-NaLuF4Tb; what is needed isThe shell layer of the rare earth core-shell nano material comprises NaYF4。
Drawings
Fig. 1 is a preparation method of a rare earth core-shell nanomaterial provided in an embodiment of the present application;
fig. 2 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 1 of the present application;
fig. 3 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 2 of the present application;
fig. 4 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 3 of the present application;
fig. 5 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 4 of the present application;
fig. 6 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 5 of the present application;
fig. 7 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 6 of the present application;
fig. 8 is a particle size distribution diagram of the rare earth core-shell nanomaterial provided in embodiment 1 of the present application;
fig. 9 is a luminescent property diagram of the rare earth core-shell nanomaterial provided in embodiment 1 of the present application;
FIG. 10 is a luminescence spectrum of the rare earth core-shell nanomaterial provided in example 1 of the present application;
fig. 11 is a living body imaging diagram of the rare earth core-shell nanomaterial provided in embodiment 1 of the present application;
fig. 12 is a biotoxicity test chart of the rare earth core-shell nanomaterial provided in example 1 of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, 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 application.
Are currently used for bioimagingThe excitation light of the soil luminescent nano material is in an infrared band, but the infrared light has the defects of poor tissue penetrability, poor stereospecificity and the like, so that the imaging effect is poor. The X-ray has good penetrability to human body, and can directly see the bone condition in the human body by penetrating the skin and the muscle without directly contacting the human body. Therefore, research and development of novel rare earth luminescent nanomaterials based on X-ray excitation are of great significance for biomedical imaging, diagnosis and treatment. In order to promote the application of the rare earth luminescent nano material in biological imaging, the application provides a rare earth core-shell nano material beta-NaLuF for realizing biological imaging by taking X rays as exciting light4:Tb@NaYF4Wherein the core body of the rare earth core-shell nano material comprises beta-NaLuF4Tb, the shell of rare earth core-shell nano material includes NaYF4。
In the application, the nuclear body beta-NaLuF of the rare earth core-shell nano material4Tb can be excited by X-rays and produces strong fluorescence. NaLuF4Tb has body-centered cubic structure (beta-) and NaLuF with body-centered cubic structure4Tb has a higher degree of crystallization and fewer surface defects, and hence the light-emitting luminance is high and the light-emitting performance is stable. Shell NaYF of rare earth core-shell nano material4The surface crystal lattice of the rare earth core-shell nano material can be perfected, the surface scattering is reduced, and the phenomenon of fluorescence quenching is inhibited, so that the energy transfer efficiency between surface ions is improved, and the rare earth core-shell nano material has higher luminous efficiency.
In the present application, beta-NaLuF4Tb represents terbium-doped lutetium sodium fluoride, wherein the molar ratio of Tb to Lu is 1 (4-99). In some embodiments of the present application, the molar ratio of Tb to Lu is 1 (4-10). Terbium is doped in the sodium lutetium fluoride, so that the luminous performance of the rare earth core-shell nano material can be adjusted, and the rare earth core-shell nano material has proper afterglow emission duration.
In the embodiment of the present application, the afterglow emission duration of the rare earth core-shell nanomaterial is 5 days to 30 days, and the afterglow emission duration of the rare earth core-shell nanomaterial may specifically be, but not limited to, 5 days, 10 days, 15 days, 20 days, 25 days, or 30 days. If the afterglow emission time of the rare earth core-shell nano material is too short, the time of the biological imaging process is short, and the imaging effect is poor; if the afterglow emission time is too long, the afterglow emission time is not favorable for subsequent imaging detection and the repeated use of the in vitro diagnosis test strip, so the afterglow emission time of the rare earth core-shell nano material is controlled to ensure that the better imaging effect is achieved and the repeated use of the in vivo multiple injections and the in vitro diagnosis test strip is not influenced.
In the embodiment of the application, the particle size of the core body of the rare earth core-shell nano material is 1-300 nm. The particle size of the core body of the rare earth core-shell nanomaterial may specifically be, but not limited to, 1nm, 10nm, 50nm, 100nm, 200nm, or 300 nm. In the embodiment of the application, the thickness of the shell of the rare earth core-shell nano material is 1-40 nm. The thickness of the shell of the rare earth core-shell nano material can be specifically but not limited to 1nm, 10nm, 30nm, 40nm or 50 nm. In the embodiment of the application, in the rare earth core-shell nano material, the ratio of the particle size of the core body to the thickness of the shell body is 1 (1-10). The ratio of the particle size of the core to the thickness of the shell may specifically be, but not limited to, 1:1, 1:3, 1:5, or 1: 10. The particle size of the core body and the thickness of the shell are controlled, so that the rare earth core-shell nano material has stable luminescence property and high luminescence efficiency.
In the embodiment of the application, the rare earth core-shell nano material is spherical particles, the spherical particles have a smaller specific surface area, the quenching effect of the particle surface on luminescent ions is small, and the luminescent efficiency of the particles is high. In the embodiment of the application, the average particle size of the rare earth core-shell nano material is 50nm-200 nm. Rare earth core-shell nano material beta-NaLuF4:Tb@NaYF4The average particle diameter of (A) may specifically be, but not limited to, 50nm, 70nm, 90nm, 95nm, 100nm, 105nm, 110nm, 130nm, 150nm or 200 nm.
The application provides a rare earth core-shell nano material beta-NaLuF4:Tb@NaYF4Can realize fluorescence emission under the excitation of X-rays, has higher luminous efficiency and stable luminous performance, and is beneficial to being applied to biological imaging.
The application also provides the rare earth core-shell nano material beta-NaLuF4:Tb@NaYF4Referring to fig. 1, fig. 1 is a method for preparing a rare earth core-shell nano material according to an embodiment of the present application,the method comprises the following steps:
step 100: carrying out first mixing treatment on a terbium salt, a lutetium salt, a base and a solvent to form a first solution;
step 200: carrying out second mixing treatment on the first solution and ammonium fluoride to obtain a second solution; placing the second solution in a hydrothermal kettle, and reacting for 1-72 h at 100-300 ℃ to obtain the rare earth core nano material;
step 300: carrying out third mixing treatment on yttrium salt, a rare earth core nano material, alkali and a solvent to form a third solution;
step 400: carrying out fourth mixing treatment on the third solution and ammonium fluoride to obtain a fourth solution; and placing the fourth solution in a hydrothermal kettle, and reacting for 1-72 h at 100-300 ℃ to obtain the rare earth core-shell nano material.
In step 100, the solvent includes water, n-butanol and oleic acid. The n-butyl alcohol can be used as a cosurfactant to promote oleic acid and water to form a microemulsion system, and the microemulsion system has a larger reaction interface, can improve the reaction rate and is beneficial to forming monodisperse nano particles with uniform structures. In the embodiment of the application, the volume ratio of the water to the n-butyl alcohol to the oleic acid is 1 (0.1-10) to 0.1-10. In some embodiments of the present application, the volume ratio of water, n-butanol and oleic acid is 1 (0.1-1): (0.1-1), and the high volume ratio of water is favorable for improving the dispersibility of the product rare earth core nanomaterial in water. Under the range of the volume ratio, an isotropic micro-emulsion system with stable thermodynamics can be formed, thereby ensuring that highly uniform and monodisperse rare earth core nano-materials are formed.
In the application, the pH value of the reaction system can be adjusted by adding alkali, so that the solubility of terbium salt and lutetium salt in the reaction system is changed, the reaction rate is controlled, and in addition, the relative growth speed of crystal faces is influenced by the pH value, so that crystals with different structures are formed. In an embodiment of the present application, the pH of the first solution is 10 to 12. Under the pH condition, the reaction is rapidly and stably performed, and the beta-NaLuF can be promoted4The Tb rare earth core-shell nano material is generated. In some embodiments of the present application, the base comprises one or more of sodium hydroxide and potassium hydroxide.
In the embodiments of the present application, the terbium salt includes one or more of terbium chloride, terbium acetate and terbium nitrate. In embodiments of the present application, the lutetium salt includes one or more of lutetium chloride, lutetium nitrate, and lutetium acetate. In the embodiment of the application, the mole ratio of the terbium salt to the lutetium salt is 1 (4-99). In some embodiments of the present application, the molar ratio of terbium salt to lutetium salt is 1 (4-10). The molar ratio of terbium salt to lutetium salt may specifically be, but not limited to, 1:4, 1:6, 1:10, 1:15, 1:20, 1:40, 1:60, or 1: 99. In the embodiment of the present application, the sum of the molar concentrations of the terbium salt and lutetium salt c1Is 0.1 mol. L-1-2mol·L-1。
In the embodiment of the application, the first mixing treatment is mixing by using probe ultrasound, the power of the probe ultrasound is 50W-500W, and the time of the probe ultrasound is 10min-30 min. In some embodiments of the present application, the power of the probe ultrasound is 50W-200W, and the time of the probe ultrasound is 15min-25 min. The ultrasonic treatment in the first mixing treatment process can promote the reactant to be uniformly dispersed in the microemulsion system, so as to ensure the stable reaction.
In some embodiments of the present application, step 100 specifically includes: mixing 0.1-4 g of sodium hydroxide with 0.1-100 mL of deionized water to form an alkali liquor; adding 0.1-100 mL of mixed solution of oleic acid and n-butanol with the volume ratio of 1 (0.1-10) into the alkali liquor to form a microemulsion system; weighing terbium salt and lutetium salt according to the molar ratio of 1 (4-99), and preparing into the total molar concentration of 0.1 mol.L-1-2mol·L-1Adding the rare earth solution into a microemulsion system, and carrying out ultrasonic treatment at 0-10 ℃ for 10-30 min to obtain a first solution.
In step 200, the sum of the molar concentrations of terbium salt and lutetium salt in the second solution, c1Molar concentration with ammonium fluoride cF1The ratio of the components is 1 (1-50). In the embodiment of the application, the second mixing treatment is mixing by using probe ultrasound, the power of the probe ultrasound is 50W-500W, and the time of the probe ultrasound is 30min-100 min. The power of the probe ultrasound in the second mixing process may specifically be, but is not limited to, 50W, 100W, 200W, 300W, 400W, or 500W. In the second mixing treatment, the ultrasound treatment may be carried out on the one handThe microemulsion system generates sharp movement including the appearance of gas nuclei, the growth of microbubbles and the burst of the microbubbles, thereby expanding the reaction interface of the microemulsion, promoting the generation and the development of the rare earth nuclear nano material and shortening the reaction time. On the other hand, ultrasonic treatment can utilize ultrasonic energy to disperse, and the particle size is controlled through a shear fracture mechanism, so that the rare earth core nano material with a uniform and monodisperse structure is formed.
In the application, the second solution is placed in a hydrothermal kettle for hydrothermal reaction, and the temperature of the hydrothermal reaction is 100-300 ℃. In some embodiments, the reaction temperature of the hydrothermal reaction is 170-250 ℃, and the rare earth core nano material with good crystallinity is formed by adopting higher reaction temperature. In the embodiment of the present application, the reaction time of the hydrothermal reaction is 1h to 72 h. In some embodiments of the present application, the reaction time of the hydrothermal reaction is 2h to 55 h. In the present embodiment, after the hydrothermal reaction is completed, the reaction vessel is cooled to room temperature, and the temperature is controlled to (1000--1Centrifuging the reaction solution for 1min-30min at the rotating speed, removing the supernatant to obtain a white precipitate, wherein the white precipitate is beta-NaLuF4Tb. In the embodiments of the present application, beta-NaLuF4The yield of Tb is 40% -60%, beta-NaLuF4The yield of Tb may be specifically, but not limited to, 40%, 50%, 55% or 60%. In some embodiments of the present application, the white precipitate is washed with ethanol, dispersed in 1mL to 50mL of water, and stored at 0 ℃ to 10 ℃.
In step 300, the solvent includes water, n-butanol and oleic acid, and the volume ratio of water, n-butanol and oleic acid is 1 (0.1-10) to 0.1-10. Under a microemulsion system, a stable shell layer is formed on the surface of the rare earth core nano material, so that the surface quenching of the rare earth core nano material is effectively inhibited, the lattice defect on the surface of the rare earth core nano material is passivated, the interference of external adverse factors is isolated, and the fluorescence efficiency of the material is greatly improved. In an embodiment of the present application, the yttrium salt comprises one or more of yttrium chloride, yttrium nitrate, and yttrium acetate, and the base comprises one or more of sodium hydroxide and potassium hydroxide. In an embodiment of the present application, the third solution has a pH of 10 to 12.
Practice of the present applicationIn the mode, the molar ratio of the yttrium salt to the rare earth core nano material in the third solution is 1 (10-100). The molar ratio of yttrium salt to rare earth core nanomaterial may specifically be, but is not limited to, 1:10, 1:30, 1:50, 1:70, or 1: 100. Under the molar ratio range, the obtained rare earth core-shell nano material has higher luminous efficiency and good stability. In the embodiment of the present application, the molar concentration of yttrium salt is 0.1 mol. L-1-2mol·L-1. The molar concentration of yttrium salt may be specifically, but not limited to, 0.1 mol. L-1、0.5mol·L-1、1mol·L-1Or 2 mol. L-1。
In the embodiment of the application, the third mixing treatment is mixing by using probe ultrasound, the power of the probe ultrasound is 50W-500W, and the time of the probe ultrasound is 10min-30 min. And in the third mixing treatment process, ultrasonic treatment can promote reactants to be uniformly dispersed in a microemulsion system, so that the reaction is stably carried out.
In some embodiments of the present application, step 300 specifically includes: mixing 0.1-4 g of sodium hydroxide with 0.1-100 mL of deionized water to form an alkali liquor; adding 0.1-100 mL of mixed solution of oleic acid and n-butanol with the volume ratio of 1 (0.1-10) into the alkali liquor to form a microemulsion system; dissolving 0.1-2 mmol of yttrium salt in 1-10 mL of water, adding the yttrium salt solution into a microemulsion system, and adding the rare earth nuclear nano material beta-NaLuF according to the molar ratio of the yttrium salt to the rare earth nuclear nano material of 1 (10-100)4Tb is added into a microemulsion system and ultrasonic treatment is carried out for 1min to 30min at the temperature of 0 ℃ to 10 ℃ to obtain a third solution.
In step 400, the molar concentration ratio of yttrium salt to ammonium fluoride in the fourth solution is 1 (1-50). The molar concentration ratio of yttrium salt to ammonium fluoride may specifically be, but not limited to, 1:1, 1:5, 1:10, 1:20, or 1: 50. In the embodiment of the application, the fourth mixing treatment is mixing by using probe ultrasound, the power of the probe ultrasound is 50W-500W, and the time of the probe ultrasound is 1min-100 min. In some embodiments of the present application, the power of the probe ultrasound is 100W-200W, and the time of the probe ultrasound is 50min-70 min. In the fourth mixing treatment process, ultrasonic treatment is carried out to enlarge the reaction interface of the microemulsion and promote NaYF4Uniform bagCovering the surface of the rare earth core nano material to form the rare earth core-shell nano material with uniform and monodisperse structure.
In the application, the fourth solution is placed in a hydrothermal kettle for hydrothermal reaction, and the temperature of the hydrothermal reaction is 100-300 ℃. In some embodiments of the present disclosure, the reaction temperature of the hydrothermal reaction is 170 ℃ to 250 ℃. In the embodiment of the present application, the reaction time of the hydrothermal reaction is 1h to 72 h. In some embodiments of the present application, the reaction time of the hydrothermal reaction is 2h to 55 h. In the present embodiment, after the hydrothermal reaction is completed, the reaction vessel is cooled to room temperature, and the temperature is controlled to (1000--1Centrifuging the reaction solution for 1min-30min at the rotating speed, removing the supernatant to obtain a white precipitate, wherein the white precipitate is NaLuF4:Tb@NaYF4And washing the white precipitate with ethanol, drying and storing. In an embodiment of the present application, in step 400, NaLuF4:Tb@NaYF4The yield of the product is 40 to 60 percent, and the NaLuF4:Tb@NaYF4The yield of (b) may be specifically but not limited to 40%, 50%, 55% or 60%.
The application synthesizes highly uniform and monodisperse NaLuF by an ultrasonic microemulsion method4:Tb@NaYF4Rare earth core-shell nano material. The method adopts the aqueous phase to synthesize the rare earth core-shell nano material, the preparation process is simple, the production cost is low, the obtained rare earth core-shell nano material has stable property and no radioactivity, does not cause harm to people and environment, can generate stronger luminous effect under the excitation of X rays, and can be used for biological imaging, thereby providing more choices for biological imaging materials.
The technical solution of the present application is further described below by a plurality of examples.
Example 1
A preparation method of a rare earth core-shell nano material comprises the following steps:
(1) synthesizing the rare earth core nano material:
a. adding 0.5g NaOH into a 50mL conical flask containing 10mL deionized water; adding 15mL of n-butanol and 5mL of oleic acid into a conical flask, immersing the ultrasonic probe of the cell disruptor into the solution, and ultrasonically treating the probe under ice bath (0℃)Forming yellow transparent microemulsion after 2 min; 0.4mmol of LuCl3·6H2O and 0.1mmol of Tb (NO)3)3Is prepared to have the concentration of 0.5 mol.L-1Adding the aqueous solution into the microemulsion, and carrying out ultrasonic treatment for 3min by using a probe under ice bath to obtain a first solution, wherein the pH value of the first solution is 12; adding 10mmol of NH4And F, adding the first solution, and carrying out ultrasonic treatment for 1h by using a probe in an ice bath to obtain a second solution, wherein the second solution is a white emulsion.
b. Placing the second solution into a 50mL polytetrafluoroethylene reaction kettle, heating at 200 deg.C for 6h, cooling to room temperature after reaction, and introducing the reaction solution into the kettle at 15000 r.min-1Centrifuging at the speed of (1) for 5min, and removing supernatant to obtain white precipitate; washing the white precipitate with ethanol for 3 times to obtain beta-NaLuF4Tb rare earth core nano material, the yield of reaction is 45%. Mixing beta-NaLuF4Tb is dispersed in 4mL of water to obtain beta-NaLuF4Tb dispersion, stored at 4 ℃.
(2) Synthesizing the rare earth core-shell nano material:
c. adding 0.5g NaOH into a 50mL conical flask containing 10mL deionized water; adding 15mL of n-butanol and 5mL of oleic acid into a conical flask, immersing an ultrasonic probe of a cell disruptor into the solution, and carrying out ultrasonic treatment on the probe for 2min under ice bath (0 ℃) to form yellow transparent microemulsion; adding 0.5mmol YCl3·6H2Dissolving O in 4mL of water to obtain an aqueous solution, adding the aqueous solution into the microemulsion, and adding the beta-NaLuF obtained in the step (1)4Adding the Tb dispersion into the microemulsion, and carrying out ultrasonic treatment for 3min by using a probe under ice bath to obtain a third solution, wherein the pH value of the third solution is 12; adding 10mmol of NH4And F, adding the third solution, and carrying out ultrasonic treatment for 1min by using a probe in an ice bath to obtain a fourth solution, wherein the fourth solution is a white emulsion.
d. Placing the fourth solution into a 50mL polytetrafluoroethylene reaction kettle, heating at 200 deg.C for 6h, cooling to room temperature after reaction, and introducing the reaction solution into the kettle at 15000 r.min-1Centrifuging at the speed of (1) for 5min, and removing supernatant to obtain precipitate; washing the precipitate with ethanol for 3 times, and oven drying to obtain beta-NaLuF4:Tb@NaYF4Rare earth core-shell nanomaterial, transThe yield should be 50%.
Example 2
A preparation method of a rare earth core-shell nano material comprises the following steps:
(1) synthesizing the rare earth core nano material:
a. adding 0.5g NaOH into a 50mL conical flask containing 10mL deionized water; adding 15mL of n-butanol and 5mL of oleic acid into a conical flask, and stirring for 20min to obtain yellow transparent microemulsion; 0.4mmol of LuCl3·6H2O and 0.1mmol of Tb (NO)3)3Is prepared to have the concentration of 0.5 mol.L-1Adding the aqueous solution into the microemulsion, and stirring for 30min to obtain a first solution; adding 10mmol of NH4And F, adding the first solution, and stirring for 1 hour to obtain a second solution, wherein the second solution is a white emulsion.
b. Placing the second solution into a 50mL polytetrafluoroethylene reaction kettle, heating at 200 deg.C for 48h, cooling to room temperature after the reaction is finished, and reacting the reaction solution at 15000 r.min-1Centrifuging at the speed of (1) for 5min, and removing supernatant to obtain white precipitate; washing the white precipitate with ethanol for 3 times to obtain beta-NaLuF4Tb rare earth core nano material, the yield of reaction is 50%. Mixing beta-NaLuF4Tb is dispersed in 4mL of water to obtain beta-NaLuF4Tb dispersion, stored at 4 ℃.
(2) Synthesizing the rare earth core-shell nano material:
c. adding 0.5g NaOH into a 50mL conical flask containing 10mL deionized water; adding 15mL of n-butanol and 5mL of oleic acid into a conical flask, and stirring for 20min to obtain yellow transparent microemulsion; adding 0.5mmol YCl3·6H2Dissolving O in 4mL of water to obtain an aqueous solution, adding the aqueous solution into the microemulsion, and adding the beta-NaLuF obtained in the step (1)4Adding Tb dispersion into microemulsion; adding 10mmol of NH4And F, adding the third solution and stirring for 1 hour to obtain a fourth solution, wherein the fourth solution is a white emulsion.
d. Placing the fourth solution into a 50mL polytetrafluoroethylene reaction kettle, heating at 200 deg.C for 48h, cooling to room temperature after the reaction is finished, and reacting the solution at 15000 r.min-1Centrifuging at the speed of (1) for 5min, and removing supernatant to obtain precipitatePrecipitating; washing the precipitate with ethanol for 3 times, and oven drying to obtain beta-NaLuF4:Tb@NaYF4The yield of the reaction of the rare earth core-shell nano material is 60 percent.
Example 3
Example 3 differs from example 1 in that in step a and step b, the volume ratio of water, oleic acid and n-butanol is 1:1: 1.
Example 4
Example 4 differs from example 1 in that in step a and step b, the volume ratio of water, oleic acid and n-butanol is 1:1: 2.
Example 5
Example 5 is different from example 1 in that the ultrasonic treatment of the probe in example 5 was carried out under room temperature conditions (25 ℃).
Example 6
Example 6 differs from example 1 in that the pH of the first solution and the third solution in example 6 is 10.
Effects of the embodiment
In order to verify the structure and the performance of the rare earth core-shell nano material prepared by the method, an effect embodiment is further provided.
1) The morphology of the rare earth core-shell nanomaterial of examples 1-6 was characterized by transmission electron microscopy.
Referring to fig. 2 to fig. 7, fig. 2 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 1 of the present application; fig. 3 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 2 of the present application; fig. 4 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 3 of the present application; fig. 5 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 4 of the present application; fig. 6 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 5 of the present application; fig. 7 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in embodiment 6 of the present application. As can be seen from FIGS. 2 to 7, the rare earth core-shell nano-materials with uniform and monodisperse structures are successfully synthesized in examples 1 to 6. Referring to fig. 8, fig. 8 is a particle size distribution diagram of the rare earth core-shell nanomaterial provided in embodiment 1 of the present application, and it can be seen from fig. 8 that the particle size distribution of the rare earth core-shell nanomaterial of embodiment 1 is concentrated in 80nm to 150nm, and the average particle size of the rare earth core-shell nanomaterial is 110 nm. The rare earth core-shell nano materials of the embodiments 2 to 6 are characterized by the same method, so as to obtain the structural parameters of the rare earth core-shell nano materials of the embodiments 2 to 6, and the characterization results refer to table 1, wherein table 1 is the structural parameter table of the rare earth core-shell nano materials of the embodiments 1 to 6.
TABLE 1 structural parameter Table for rare earth core-shell nanomaterials of examples 1-6
Experimental group Average particle diameter (nm) Thickness of shell (nm)
Example 1 110 20
Example 2 200 30
Example 3 150 25
Example 4 200 30
Example 5 120 20
Example 6 150 27
2) The luminescent property of the rare earth core-shell nano material of the embodiment 1 is tested, and the test process specifically comprises the following steps: beta-NaLuF from example 14:Tb@NaYF4The rare earth core-shell nano material is dispersed in water, the mass concentration of the dispersion liquid is 10mg/mL, 100 mu L of the dispersion liquid is placed under the X-ray with the radiation dose of 10Gy for irradiation, and the luminescence condition is recorded after the irradiation. Referring to fig. 9, fig. 9 is a luminescent performance diagram of the rare earth core-shell nano material provided in embodiment 1 of the present application, and it can be seen from fig. 9 that after the X-ray source is turned off, β -NaLuF is performed4:Tb@NaYF4The rare earth core-shell nano material has obvious afterglow luminescence within 0-14 days, the afterglow becomes weak along with the afterglow, the afterglow is basically invisible within 28 days, and the proper afterglow emission time is favorable for subsequent imaging detection and repeated use of in-vitro diagnosis test paper strips.
The luminescent property of the rare earth core-shell nano material is tested by adopting a fluorescence spectrometer, and the test process specifically comprises the following steps: beta-NaLuF from example 14:Tb@NaYF4The rare earth core-shell nano material is dispersed in water, the mass concentration of the dispersion liquid is 10mg/mL, 100 mu L of the dispersion liquid is placed under an X ray with the radiation dose of 10Gy for irradiation, and the luminescence spectrum of the rare earth core-shell nano material is measured by a fluorescence spectrometer after the irradiation for half an hour. Referring to fig. 10, fig. 10 is a luminescence spectrum of the rare earth core-shell nanomaterial provided in embodiment 1 of the present application, and as can be seen from fig. 10, emission peak wavelengths of the rare earth core-shell nanomaterial are 490nm, 540nm, 580nm, and 620 nm.
After 100 μ L of the dispersion liquid of the rare earth core-shell nanomaterial is irradiated under X-ray with a radiation dose of 10Gy, the dispersion liquid is injected into a mouse body subcutaneously, and luminescence detection (detection of emitted light without excitation light) is performed by living body imaging of a small animal, please refer to fig. 11, which is a living body imaging diagram of the rare earth core-shell nanomaterial provided in embodiment 1 of the present application. As can be seen from fig. 11, the rare earth core-shell nanomaterial has strong luminescence property, and the state of the organism can be clearly observed, thereby realizing effective treatment.
3) The biotoxicity of the rare earth core-shell nano material in the embodiment 1 is tested, and the testing process specifically comprises the following steps: the rare earth core-shell nanomaterial obtained in example 1 is prepared into a dispersion, the dispersion is injected into a mouse body as an experimental group by tail vein injection according to the amount of 10mg/kg, a control group is injected with Phosphate Buffer Solution (PBS), after one week, each organ of the mouse is taken for HE staining, please refer to fig. 12, fig. 12 is a biological toxicity test chart of the rare earth core-shell nanomaterial provided in example 1 of the present application, and it can be seen from fig. 12 that each organ tissue of the mouse is normal after the dispersion is injected, that is, the rare earth core-shell nanomaterial has no toxicity to organisms.
The foregoing is illustrative of the preferred embodiments of the present application and is not to be construed as limiting the scope of the application. It should be noted that, for those skilled in the art, without departing from the principle of the present application, several improvements and modifications can be made, and these improvements and modifications are also considered to be within the scope of the present application.

Claims (10)

1. The preparation method of the rare earth core-shell nano material is characterized by comprising the following steps:
carrying out first mixing treatment on a terbium salt, a lutetium salt, a base and a solvent to form a first solution; the solvent comprises water, n-butanol and oleic acid in a volume ratio of 1 (0.1-10) to (0.1-10);
carrying out second mixing treatment on the first solution and ammonium fluoride to obtain a second solution; placing the second solution in a hydrothermal kettle, and reacting at 100-300 ℃ for 1-72 h to obtain the rare earth core nano material; the rare earth core nano material comprises beta-NaLuF4:Tb；
Carrying out third mixing treatment on yttrium salt, the rare earth core nano material, the alkali and the solvent to form a third solution;
carrying out fourth mixing treatment on the third solution and ammonium fluoride to obtain a fourth solution; putting the fourth solution into a hydrothermal kettle, and reacting for 1-72 h at 100-300 ℃ to obtain the rare earth core-shellThe shell layer of the rare earth core-shell nano material comprises NaYF4。
2. The method according to claim 1, wherein the first mixing treatment, the second mixing treatment, the third mixing treatment, and the fourth mixing treatment are mixed using probe ultrasound having a power of 50W to 500W.
3. The production method according to claim 1 or 2, wherein the temperature of the first mixing treatment, the second mixing treatment, the third mixing treatment, and the fourth mixing treatment is 0 ℃ to 10 ℃.
4. The production method according to any one of claims 1 to 3, wherein the pH of the first solution and the third solution is 10 to 12.
5. The process according to any one of claims 1 to 4, wherein the volume ratio of n-butanol to oleic acid is 1 (0.1 to 10).
6. The method of any one of claims 1-5, wherein the molar ratio of the terbium salt to the lutetium salt in the first solution is 1 (4-99).
7. The method of any one of claims 1-6, wherein the sum of the molar concentrations of the terbium salt and the lutetium salt c in the first solution1Is 0.1 mol. L-1-2mol·L-1(ii) a The sum of the molar concentrations of the terbium salt and the lutetium salt in the second solution c1With the molar concentration c of the ammonium fluorideF1The ratio of the components is 1 (1-50).
8. The method of any of claims 1-7, wherein the molar concentration of yttrium salt in the third solution is 0.1 mol-L-1-2mol·L-1(ii) a The yttriumThe molar ratio of the salt to the rare earth core nano material is 1 (10-100).
9. The production method according to any one of claims 1 to 8, wherein the molar concentration ratio of the yttrium salt to the ammonium fluoride in the fourth solution is 1 (1) to 50.
10. The rare earth core-shell nano material is characterized by being prepared by the preparation method of any one of claims 1 to 9, and comprising a rare earth core nano material and a shell layer coated on the surface of the rare earth core nano material; the rare earth core nano material comprises beta-NaLuF4Tb; the shell layer of the rare earth core-shell nano material comprises NaYF4。
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