CN112898977A - Terbium ion doped up-conversion nano material and preparation method thereof - Google Patents
Terbium ion doped up-conversion nano material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of luminescent materials, and particularly relates to red light-emitting terbium ion-doped Ho3+A base up-conversion nano material and a preparation method thereof. The upconversion nano material is prepared by NaHoF4Is a core layer, and is coated with NaYF in turn4Tb shell layer, NaYbF4Tb shell and NaYF4Passivation layer, in turn using Tb3+:5D4Energy transfer between energy levels and Tb3+:5D4Energy level pair Ho3+:5S2/5F4Interfacial energy transfer of energy levels, transfer of excitation energy from the second shell layer to the core layer, and induce Ho3+Effect of cross relaxation between ions: (5S2/5F4+5I7→5F5+5I6) Finally, Ho is obtained3+The red light emission is converted on the basis. The up-conversion nano material has the advantages of simple preparation process, low equipment cost, easy operation and short preparation period, and is suitable for mass production.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to red light-emitting terbium ion-doped Ho3+A base up-conversion nano material and a preparation method thereof.
Background
Up-conversion luminescence also known as anti-stokes luminescenceThis means a process of converting excitation light having a long wavelength into emission light having a short wavelength by multiphoton absorption. The up-conversion nano material has the advantages of narrow emission band, rich emission energy level, high chemical stability, low toxicity and the like, and has wide application prospects in the aspects of biomedical imaging, anti-counterfeiting, fluorescent coding labels, super-resolution nano microscopes and the like. In the visible light range, red light (600-700nm) has relatively high biological tissue penetrability due to relatively long wavelength, and is known as an optical window. Furthermore, Ho3+The ion is an excellent activating ion, and the red light emission converted on the ion has prominent performance in the biomedical field. However, Ho3+The biggest problem with base materials is the high concentration of Ho3+Fluorescence quenching induced by doping. In addition, the large size also limits its application in the biological field. Therefore, how to develop a small-sized Ho3+The basic conversion red light emitting nanometer material is one of the great difficulties in the present luminescent material technology.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a terbium ion-doped up-conversion nanomaterial, which is red light-emitting terbium ion-doped Ho3+And converting the nano material on the basis. The average size of the nano material is 10.21nm, and the nano material belongs to the core-shell structure design, namely, NaHoF4@NaYF4:xTb@NaYbF4:yTb@NaYF4The structural design sequentially utilizes Tb3+Energy transfer and Tb3+To Ho3+To finally obtain Ho3+The red light emission is converted on the basis.
The invention also aims to provide a preparation method of the terbium ion-doped up-conversion nano material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
terbium ion doped up-conversion nano material with chemical expression of NaHoF4@NaYF4:xTb@NaYbF4:yTb@NaYF4I.e. with NaHoF4Is a core layer, and is coated with NaYF4xTb shell layer, NaYbF4yTb Shell layer and NaYF4A passivation layer;
wherein x is Tb/(Tb + Y) molar concentration; Tb/(Tb + Yb) molar concentration.
Preferably, the value of x is 73.5-76.5%.
More preferably, the value of x is 75%.
Preferably, the value of y is 28.5-31.5%.
More preferably, the value of y is 30%.
Preferably, the particle size of the up-conversion nano material is 8.5-12.5 nm.
More preferably, the particle size of the upconversion nanomaterial is 10.21 nm.
The invention further provides a preparation method of the terbium ion-doped up-conversion nano material, which comprises the following steps:
(1)NaHoF4preparation of the core layer: mixing and stirring oleic acid and octadecene uniformly, adding holmium chloride solution, mixing and stirring uniformly, heating to remove moisture, performing high-temperature reaction to generate rare earth-oleic acid chelate, cooling to normal temperature, adding methanol solution of sodium hydroxide and ammonium fluoride, stirring, heating to remove redundant methanol, performing high-temperature reaction under the protection of argon, washing and centrifuging the reacted turbid solution to obtain white precipitate, namely obtaining nuclear layer NaHoF4A nanoparticle;
(2)NaYF4xTb shell coating: mixing and stirring oleic acid, octadecene, yttrium-oleic acid chelate and terbium-oleic acid chelate uniformly, and then adding the core layer NaHoF prepared in the step (1)4Adding a methanol solution of sodium hydroxide and ammonium fluoride into the nano particles, stirring, heating to remove redundant methanol, carrying out high-temperature reaction under the protection of argon, and naturally cooling to obtain the product containing NaHoF4@NaYF4xTb a reaction solution of core-shell structured nanoparticles;
(3)NaYbF4yTb shell coating: adding ytterbium-oleic acid chelate and terbium-oleic acid chelate into the reaction solution obtained in the step (2), and uniformly stirring; then adding a methanol solution of sodium hydroxide and ammonium fluoride andstirring, heating to remove excessive methanol, performing high-temperature reaction under the protection of argon, and naturally cooling to obtain the product containing NaHoF4@NaYF4:xTb@NaYbF4yTb reaction solution of core-shell structured nanoparticles;
(4)NaYF4and (3) coating a passivation layer: adding yttrium-oleic acid chelate into the reaction solution obtained in the step (3), and uniformly stirring; and then adding methanol solution of sodium hydroxide and ammonium fluoride, stirring, heating to remove redundant methanol, carrying out high-temperature reaction under the protection of argon, and finally washing and centrifuging the reacted turbid solution to obtain the terbium ion-doped up-conversion nano material.
Preferably, the core layer NaHoF is obtained in the step (1)4And (4) storing the nanoparticles and the terbium ion-doped up-conversion nanomaterial obtained in the step (4) in cyclohexane before use.
Preferably, the volume ratio of the oleic acid to the octadecene in the step (1) is 0.68: 1-0.82: 1.
More preferably, the volume ratio of oleic acid to octadecene in step (1) is 0.75: 1.
Preferably, the concentration of the holmium chloride solution in the step (1) is 0.85-1.15 mol.L-1。
More preferably, the concentration of the holmium chloride solution in the step (1) is 1 mol.L-1。
Preferably, the volume ratio of the oleic acid to the holmium chloride solution in the step (1) is 13: 1-17: 1.
Preferably, the volume ratio of the oleic acid to the holmium chloride solution in the step (1) is 15: 1.
Preferably, the temperature for raising the temperature to remove the water in the step (1) is 98-112 ℃.
More preferably, the temperature for removing water by raising the temperature in the step (1) is 105 ℃.
Preferably, the condition for generating the rare earth-oleic acid chelate through the high-temperature reaction in the step (1) is that the reaction is carried out for 30-50 min at 148-152 ℃.
More preferably, the high temperature reaction in step (1) to form the rare earth-oleic acid chelate is carried out at 150 ℃ for 40 min.
Preferably, in the methanol solution of sodium hydroxide and ammonium fluoride in the step (1), the concentration of sodium hydroxide is 0.23-0.27 mol/L.
More preferably, in the methanol solution of sodium hydroxide and ammonium fluoride in the step (1), the concentration of sodium hydroxide is 0.25 mol/L.
Preferably, in the methanol solution of sodium hydroxide and ammonium fluoride in the step (1), the concentration of ammonium fluoride is 0.39-0.41 mol/L.
More preferably, in the methanol solution of sodium hydroxide and ammonium fluoride in the step (1), the concentration of ammonium fluoride is 0.4 mol/L.
Preferably, the volume ratio of the holmium chloride solution to the methanol solution of sodium hydroxide and ammonium fluoride in the step (1) is 1: 8-1: 12.
More preferably, the volume ratio of the holmium chloride solution to the methanol solution of sodium hydroxide and ammonium fluoride in the step (1) is 1: 10.
Preferably, the concentration of the terbium-oleic acid chelate in the step (2) and the step (3) is 0.038-0.042 mol.L-1。
More preferably, the concentration of the terbium-oleic acid chelate compound in the step (2) and the step (3) is 0.04 mol.L-1。
Preferably, the concentration of the yttrium-oleic acid chelate in the step (2) and the step (4) is 0.038-0.042 mol.L-1。
More preferably, the concentration of the yttrium-oleic acid chelate complex in the step (2) and the step (4) is 0.04 mol.L-1。
Preferably, the volume ratio of the oleic acid to the yttrium-oleic acid chelate in the step (2) is 1: 0.06-1: 0.065.
More preferably, the volume ratio of oleic acid to yttrium-oleic acid chelate complex in step (2) is 1: 0.0625.
Preferably, the core layer is NaHoF described in step (2)4The molar ratio of the nanoparticles to the yttrium-oleic acid chelate is 1: 0.2-1: 0.3.
More preferably, the core layer is a NaHoF layer as described in step (2)4Nanoparticles with Yttrium-oleic acidThe molar ratio of the chelate is 1: 0.25.
Preferably, in the methanol solution of sodium hydroxide and ammonium fluoride in the step (2), the step (3) and the step (4), the concentration of sodium hydroxide is 0.038-0.046 mol/L.
More preferably, in the methanol solution of sodium hydroxide and ammonium fluoride described in step (2), step (3) and step (4), the concentration of sodium hydroxide is 0.042 mol/L.
Preferably, in the methanol solution of sodium hydroxide and ammonium fluoride in the step (2), the step (3) and the step (4), the concentration of ammonium fluoride is 0.062-0.072 mol/L.
More preferably, in the methanol solution of sodium hydroxide and ammonium fluoride described in step (2), step (3) and step (4), the concentration of ammonium fluoride is 0.067 mol/L.
Preferably, the volume ratio of the yttrium-oleic acid chelate in the step (2) to the methanol solution of sodium hydroxide and ammonium fluoride is 1: 9.2-1: 10.
More preferably, the volume ratio of the yttrium-oleic acid chelate complex to the methanol solution of sodium hydroxide and ammonium fluoride in the step (2) is 1: 9.6.
Preferably, the concentration of the ytterbium-oleic acid chelate in the step (3) is 0.038-0.042 mol.L-1。
More preferably, the concentration of ytterbium-oleic acid chelate compound in the step (3) is 0.04mol · L-1。
Preferably, the terbium-oleic acid chelate complex described in the step (3) and the core layer NaHoF described in the step (2)4The mole ratio of the nano particles is 0.1: 1-0.5: 1.
More preferably, the terbium-oleic acid chelate complex described in step (3) and the core layer NaHoF described in step (2)4The molar ratio of the nanoparticles was 0.3: 1.
Preferably, the volume ratio of the methanol solution of sodium hydroxide and ammonium fluoride to the terbium-oleic acid chelate in the step (3) is 6: 1-10: 1.
More preferably, the volume ratio of the methanol solution of sodium hydroxide and ammonium fluoride to the terbium-oleic acid chelate in the step (3) is 8: 1.
Preferably, step (4)) The yttrium-oleic acid chelate complex of (1) and the core layer NaHoF of (2)4The mole ratio of the nano particles is 0.8: 1-1.2: 1.
More preferably, the yttrium-oleic acid chelate complex of step (4) is complexed with the core layer NaHoF of step (2)4The molar ratio of the nanoparticles was 1: 1.
Preferably, the volume ratio of the methanol solution of sodium hydroxide and ammonium fluoride to the yttrium-oleic acid chelate in the step (4) is 2: 1-2.8: 1.
More preferably, the volume ratio of the methanolic solution of sodium hydroxide and ammonium fluoride to yttrium-oleic acid chelate complex described in step (4) is 2.4: 1.
Preferably, the temperature for removing the excessive methanol by raising the temperature in the step (1), the step (2), the step (3) and the step (4) is 88-92 ℃.
More preferably, the temperature for removing the excessive methanol by raising the temperature in the step (1), the step (2), the step (3) and the step (4) is 90 ℃.
Preferably, the high-temperature reaction conditions in the step (1), the step (2), the step (3) and the step (4) are that the reaction is carried out for 0.98-1.02 h at 278-282 ℃.
More preferably, the high temperature reaction conditions in step (1), step (2), step (3) and step (4) are reaction at 280 ℃ for 1 h.
Preferably, the washing manner in the step (1) and the step (4) is washing with absolute ethyl alcohol.
Preferably, the centrifugation conditions in the step (1) and the step (4) are that the centrifugation is carried out for 9.5-10.5 min at 8500-11500 r/min for 2-4 times.
More preferably, the centrifugation conditions in step (1) and step (4) are centrifugation at 10000 rpm for 10min for 3 times.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the upconversion nano material prepared by the invention is NaHoF4Is a core layer, and is coated with NaYF in turn4xTb shell layer, NaYbF4yTb Shell layer and NaYF4And a passivation layer. The structural design sequentially utilizes Tb3+Energy transfer and Tb3+To Ho3+Transfer of excitation energy from the second shell layer to the core layer and induce Ho3+Cross relaxation effect between ions to finally obtain Ho3+The red light emission is converted on the basis.
(2) According to the preparation method, oleic acid, octadecene, rare earth chloride, rare earth-oleic acid chelate, sodium hydroxide and ammonium fluoride are subjected to simple coprecipitation reaction, and the up-conversion nano material can be prepared. The preparation process is simple, low in equipment cost, easy to operate, short in preparation period and suitable for mass production.
Drawings
FIG. 1 is a NaHoF prepared in example 14@NaYF4:75％Tb@NaYbF4:30％Tb@NaYF4A transmission electron micrograph (a) and a selected area electron diffraction micrograph (b) of the up-converted nanomaterial.
FIG. 2 is a NaHoF prepared in example 14@NaYF4:75％Tb@NaYbF4:30％Tb@NaYF4And (3) converting the fluorescence spectrum of the nano material.
FIG. 3 is a NaHoF prepared in example 14@NaYF4:75％Tb@NaYbF4:30％Tb@NaYF4And (3) an up-conversion level transition diagram of the up-conversion nano material under the excitation of 980 nm.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
This example provides a NaHoF4@NaYF4:75％Tb@NaYbF4:30％Tb@NaYF4A method for preparing up-conversion nano material.
(1)NaHoF4Preparation of a nuclear layer: 15mL of oleic acid and 20mL of octadecene were put into a 100mL three-necked flask, and mixed and stirred uniformly. Then 1mL of 1 mol. L of a solution was added-1The holmium chloride solution is mixed and stirred uniformly, then the temperature is raised to 105 ℃ and kept for 40min, and the water is removed. Then the temperature is adjustedRaising the temperature to 150 ℃ and keeping the temperature for 40min to generate the rare earth-oleic acid chelate. The temperature was then allowed to cool to room temperature, 0.1g of sodium hydroxide (2.5mmol) and 0.148g of ammonium fluoride (4mmol) in methanol (10 mL in total) were added to the mixture and stirred, followed by warming to 90 ℃ and holding for 1h, and excess methanol was removed. The temperature was then raised to 280 ℃ for 1h under argon. Finally, the reacted turbid solution is naturally cooled to room temperature, washed by absolute ethyl alcohol, and centrifuged for 10min at 10000 r/min for three times to obtain white precipitate, namely NaHoF4Nanoparticles (as a core layer) and stored in cyclohexane.
(2)NaYF475% of Tb shell coating: 10mL of oleic acid and 15mL of octadecene were put into a 100mL three-necked flask, and mixed and stirred uniformly. Then 0.625mL of a 0.04 mol.L solution was added-1And 1.875mL of yttrium-oleic acid chelate having a concentration of 0.04 mol.L-1Mixing and stirring the terbium-oleic acid chelate uniformly. Followed by the addition of 0.1mmol of NaHoF4Nanoparticles, then 0.01g of sodium hydroxide (0.25mmol) and 0.0148g of ammonium fluoride (0.4mmol) in methanol (6 mL in total) were added to the above mixture and stirred, followed by warming to 90 ℃ and holding for 40min, and excess methanol was removed. Then raising the temperature to 280 ℃ for reaction for 1h under the protection of argon, and then naturally cooling to obtain the product containing NaHoF4@NaYF475% of Tb core-shell structured nanoparticles.
(3)NaYbF430% of Tb shell coating: 1.75mL of the solution was added at a concentration of 0.04 mol. L-1Ytterbium-oleic acid chelate of (2) and a concentration of 0.75mL of 0.04 mol. L-1And (3) adding the terbium-oleic acid chelate into the reaction solution naturally cooled in the step (2), and uniformly stirring. Then, a solution of 0.01g of sodium hydroxide (0.25mmol) and 0.0148g of ammonium fluoride (0.4mmol) in methanol (6 mL in total) was added to the above mixture and stirred, followed by warming to 90 ℃ and holding for 40min to remove excess methanol. Then raising the temperature to 280 ℃ for reaction for 1h under the protection of argon, and then naturally cooling to obtain the product containing NaHoF4@NaYF4:75％Tb@NaYbF430% of Tb core-shell structured nanoparticles.
(4)NaYF4Coating a shell layer: will be provided with2.5mL of the solution had a concentration of 0.04 mol. L-1And (3) adding the yttrium-oleic acid chelate into the reaction solution naturally cooled in the step (3), and uniformly stirring. Then, a solution of 0.01g of sodium hydroxide (0.25mmol) and 0.0148g of ammonium fluoride (0.4mmol) in methanol (6 mL in total) was added to the above mixture and stirred, followed by warming to 90 ℃ and holding for 40min to remove excess methanol. The temperature was then raised to 280 ℃ for 1h under argon. Finally, the reacted turbid solution is naturally cooled to room temperature, washed by absolute ethyl alcohol, and centrifuged for 10min at 10000 r/min for three times to obtain white precipitate, namely NaHoF4@NaYF4:75％Tb@NaYbF4:30％Tb@NaYF4Core-shell structured nanoparticles and stored in cyclohexane.
Example 2
This example provides a NaHoF4@NaYF4:73.5％Tb@NaYbF4:28.5％Tb@NaYF4A method for preparing up-conversion nano material.
(1)NaHoF4Preparation of a nuclear layer: 13.6mL of oleic acid and 20mL of octadecene were put into a 100mL three-necked flask, and mixed and stirred uniformly. Then 1mL of 1 mol. L of a solution was added-1The holmium chloride solution is mixed and stirred uniformly, then the temperature is raised to 98 ℃ and kept for 40min, and the water is removed. Then the temperature is raised to 148 ℃ and kept for 40min to generate rare earth-oleic acid chelate. The temperature was then allowed to cool to room temperature and 0.1g of sodium hydroxide (2.5mmol) and 0.148g of ammonium fluoride (4mmol) in methanol (10 mL in total) were added to the mixture and stirred, then warmed to 88 ℃ and held for 1h to remove excess methanol. The temperature was then raised to 278 ℃ for 1h under argon. Finally, the reacted turbid solution is naturally cooled to room temperature, washed by absolute ethyl alcohol, and centrifuged for 10min at 10000 r/min for three times to obtain white precipitate, namely NaHoF4Nanoparticles (as a core layer) and stored in cyclohexane.
(2)NaYF473.5 percent of Tb shell coating: 10mL of oleic acid and 15mL of octadecene were put into a 100mL three-necked flask, and mixed and stirred uniformly. Then 0.663mL of 0.04 mol.L was added-1And 1.838mL of 0.04m concentrationol·L-1Mixing and stirring the terbium-oleic acid chelate uniformly. Followed by the addition of 0.1mmol of NaHoF4Nanoparticles, then 0.01g of sodium hydroxide (0.25mmol) and 0.0148g of ammonium fluoride (0.4mmol) in methanol (6 mL in total) were added to the above mixture and stirred, followed by warming to 88 ℃ and holding for 40min, and excess methanol was removed. Then the temperature is increased to 278 ℃ to react for 1h under the protection of argon, and then the reaction product is naturally cooled to obtain the product containing NaHoF4@NaYF473.5 percent of Tb core-shell structured nano-particles.
(3)NaYbF428.5 percent of Tb shell coating: 1.788mL of the solution was added to a concentration of 0.04 mol. L-1Ytterbium-oleic acid chelate complex and 0.712mL of a concentration of 0.04 mol. L-1And (3) adding the terbium-oleic acid chelate into the reaction solution naturally cooled in the step (2), and uniformly stirring. Then, a solution of 0.01g of sodium hydroxide (0.25mmol) and 0.0148g of ammonium fluoride (0.4mmol) in methanol (6 mL in total) was added to the above mixture and stirred, followed by warming to 88 ℃ and holding for 40min to remove excess methanol. Then the temperature is increased to 278 ℃ to react for 1h under the protection of argon, and then the reaction product is naturally cooled to obtain the product containing NaHoF4@NaYF4:73.5％Tb@NaYbF428.5% of a reaction solution of Tb core-shell structured nanoparticles.
(4)NaYF4Coating a shell layer: 2.5mL of the solution was added at a concentration of 0.04 mol. L-1And (3) adding the yttrium-oleic acid chelate into the reaction solution naturally cooled in the step (3), and uniformly stirring. Then, a solution of 0.01g of sodium hydroxide (0.25mmol) and 0.0148g of ammonium fluoride (0.4mmol) in methanol (6 mL in total) was added to the above mixture and stirred, followed by warming to 88 ℃ and holding for 40min to remove excess methanol. The temperature was then raised to 278 ℃ for 1h under argon. Finally, the reacted turbid solution is naturally cooled to room temperature, washed by absolute ethyl alcohol, and centrifuged for 10min at 10000 r/min for three times to obtain white precipitate, namely NaHoF4@NaYF4:73.5％Tb@NaYbF4:28.5％Tb@NaYF4Core-shell structured nanoparticles and stored in cyclohexane.
Example 3
This example provides a NaHoF4@NaYF4:76.5％Tb@NaYbF4:31.5％Tb@NaYF4A method for preparing up-conversion nano material.
(1)NaHoF4Preparation of a nuclear layer: 16.4mL of oleic acid and 20mL of octadecene were put into a 100mL three-necked flask, and mixed and stirred uniformly. Then 1mL of 1 mol. L of a solution was added-1The holmium chloride solution is mixed and stirred uniformly, then the temperature is raised to 112 ℃ and kept for 40min, and the water is removed. Then the temperature is raised to 152 ℃ and kept for 40min to generate rare earth-oleic acid chelate. The temperature was then allowed to cool to room temperature and 0.1g of sodium hydroxide (2.5mmol) and 0.148g of ammonium fluoride (4mmol) in methanol (10 mL in total) were added to the mixture and stirred, then warmed to 92 ℃ and held for 1h to remove excess methanol. The temperature was then raised to 282 ℃ for 1h under argon. Finally, the reacted turbid solution is naturally cooled to room temperature, washed by absolute ethyl alcohol, and centrifuged for 10min at 10000 r/min for three times to obtain white precipitate, namely NaHoF4Nanoparticles (as a core layer) and stored in cyclohexane.
(2)NaYF476.5 percent of Tb shell coating: 10mL of oleic acid and 15mL of octadecene were put into a 100mL three-necked flask, and mixed and stirred uniformly. Then 0.588mL of a 0.04 mol.L solution was added-1Yttrium-oleic acid chelate of (1.912 mL) at a concentration of 0.04 mol. L-1Mixing and stirring the terbium-oleic acid chelate uniformly. Followed by the addition of 0.1mmol of NaHoF4Nanoparticles, then 0.01g of sodium hydroxide (0.25mmol) and 0.0148g of ammonium fluoride (0.4mmol) in methanol (6 mL in total) were added to the above mixture and stirred, followed by warming to 92 ℃ and holding for 40min, and excess methanol was removed. Then raising the temperature to 282 ℃ under the protection of argon gas for reaction for 1h, and then naturally cooling to obtain the product containing NaHoF4@NaYF476.5% Tb core-shell structured nanoparticles.
(3)NaYbF431.5 percent of Tb shell coating: 1.713mL of the solution was added at a concentration of 0.04 mol. L-1Ytterbium-oleic acid chelate complex and 0.787mL of a concentration of 0.04 mol. L-1And (3) adding the terbium-oleic acid chelate into the reaction solution naturally cooled in the step (2), and uniformly stirring. Then 0.01g of sodium hydroxide (0.25mmol) and0.0148g of a methanol solution (total of 6mL) of ammonium fluoride (0.4mmol) was added to the above mixture and stirred, followed by warming to 92 ℃ and holding for 40min to remove excess methanol. Then raising the temperature to 282 ℃ under the protection of argon gas for reaction for 1h, and then naturally cooling to obtain the product containing NaHoF4@NaYF4:76.5％Tb@NaYbF431.5% of Tb core-shell structured nanoparticles.
(4)NaYF4Coating a shell layer: 2.5mL of the solution was added at a concentration of 0.04 mol. L-1And (3) adding the yttrium-oleic acid chelate into the reaction solution naturally cooled in the step (3), and uniformly stirring. Then, a solution of 0.01g of sodium hydroxide (0.25mmol) and 0.0148g of ammonium fluoride (0.4mmol) in methanol (6 mL in total) was added to the above mixture and stirred, followed by warming to 92 ℃ and holding for 40min to remove excess methanol. The temperature was then raised to 282 ℃ for 1h under argon. Finally, the reacted turbid solution is naturally cooled to room temperature, washed by absolute ethyl alcohol, and centrifuged for 10min at 10000 r/min for three times to obtain white precipitate, namely NaHoF4@NaYF4:76.5％Tb@NaYbF4:31.5％Tb@NaYF4Core-shell structured nanoparticles and stored in cyclohexane.
Transmission Electron microscopy was used to align the NaHoF prepared in example 14@NaYF4:75％Tb@NaYbF4:30％Tb@NaYF4The morphology and selected area electron diffraction analysis of the up-conversion nano material is carried out, and the results are shown in fig. 1(a) and (b), which proves that the obtained nano material has high uniformity and dispersity, and the average size is 10.21 nm; in addition, the nanomaterial has a pure hexagonal phase lattice structure. The NaHoF prepared in example 1 was analyzed by a fluorescence analyzer4@NaYF4:75％Tb@NaYbF4:30％Tb@NaYF4The fluorescence spectrum of the up-conversion nano material under the excitation of 980nm is analyzed as shown in figure 2, and therefore, we obtain Ho3+The red light emission is converted on the basis. FIG. 3 is a NaHoF prepared in example 14@NaYF4:75％Tb@NaYbF4:30％Tb@NaYF4The transition diagram of the up-conversion level of the up-conversion nano material under the excitation of 980nm can be seen by using NaHoF4Is a nuclear layerAnd sequentially coating NaYF outside the shell4xTb shell layer, NaYbF4yTb Shell layer and NaYF4Passivation layer, which can utilize Tb in turn3+:5D4Energy transfer between energy levels and Tb3+:5D4Energy level pair Ho3+:5S2/5F4Interfacial energy transfer of energy levels, transfer of excitation energy from the second shell layer to the core layer, and induce Ho3+Effect of cross relaxation between ions: (5S2/5F4+5I7→5F5+5I6) Finally, Ho is obtained3+The red light emission is converted on the basis.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A terbium ion-doped up-conversion nano material is characterized in that: the chemical expression is NaHoF4@NaYF4:xTb@NaYbF4:yTb@NaYF4I.e. with NaHoF4Is a core layer, and is coated with NaYF4xTb shell layer, NaYbF4yTb Shell layer and NaYF4A passivation layer;
wherein x is Tb/(Tb + Y) molar concentration; Tb/(Tb + Yb) molar concentration.
2. The terbium ion doped upconversion nanomaterial according to claim 1, wherein:
the value of x is 73.5-76.5%;
the value of y is 28.5-31.5%.
3. The terbium ion-doped upconversion nanomaterial according to claim 2, wherein:
the value of x is 75%;
the value of y is 30%.
4. The terbium ion-doped upconversion nanomaterial according to any one of claims 1 to 3, wherein: the particle size of the up-conversion nano material is 8.5-12.5 nm.
5. The method for preparing a terbium ion doped upconversion nanomaterial according to any one of claims 1 to 4, comprising the steps of:
(1)NaHoF4preparation of the core layer: mixing and stirring oleic acid and octadecene uniformly, adding holmium chloride solution, mixing and stirring uniformly, heating to remove moisture, performing high-temperature reaction to generate rare earth-oleic acid chelate, cooling to normal temperature, adding methanol solution of sodium hydroxide and ammonium fluoride, stirring, heating to remove redundant methanol, performing high-temperature reaction under the protection of argon, washing and centrifuging the reacted turbid solution to obtain white precipitate, namely obtaining nuclear layer NaHoF4A nanoparticle;
(2)NaYF4xTb shell coating: mixing and stirring oleic acid, octadecene, yttrium-oleic acid chelate and terbium-oleic acid chelate uniformly, and then adding the core layer NaHoF prepared in the step (1)4Adding a methanol solution of sodium hydroxide and ammonium fluoride into the nano particles, stirring, heating to remove redundant methanol, carrying out high-temperature reaction under the protection of argon, and naturally cooling to obtain the product containing NaHoF4@NaYF4xTb a reaction solution of core-shell structured nanoparticles;
(3)NaYbF4yTb shell coating: adding ytterbium-oleic acid chelate and terbium-oleic acid chelate into the reaction solution obtained in the step (2), and uniformly stirring; then adding methanol solution of sodium hydroxide and ammonium fluoride, stirring, heating to remove excessive methanol, carrying out high-temperature reaction under the protection of argon, and naturally cooling to obtain the product containing NaHoF4@NaYF4:xTb@NaYbF4yTb reaction solution of core-shell structured nanoparticles;
(4)NaYF4and (3) coating a passivation layer: chelate of yttrium-oleic acidAdding the mixture into the reaction solution obtained in the step (3), and uniformly stirring; and then adding methanol solution of sodium hydroxide and ammonium fluoride, stirring, heating to remove redundant methanol, carrying out high-temperature reaction under the protection of argon, and finally washing and centrifuging the reacted turbid solution to obtain the terbium ion-doped up-conversion nano material.
6. The terbium ion doped upconversion nanomaterial according to claim 5, wherein:
the condition for generating the rare earth-oleic acid chelate by the high-temperature reaction in the step (1) is that the reaction is carried out for 30-50 min at 148-152 ℃;
the high-temperature reaction conditions in the step (1), the step (2), the step (3) and the step (4) are that the reaction is carried out for 0.98-1.02 h at 278-282 ℃.
7. The terbium ion doped upconversion nanomaterial according to claim 5, wherein:
the nuclear layer NaHoF in the step (2)4The molar ratio of the nanoparticles to the yttrium-oleic acid chelate is 1: 0.2-1: 0.3;
the terbium-oleic acid chelate in the step (3) and the nuclear layer NaHoF in the step (2)4The mole ratio of the nano particles is 0.1: 1-0.5: 1;
the yttrium-oleic acid chelate in the step (4) and the nuclear layer NaHoF in the step (2)4The mole ratio of the nano particles is 0.8: 1-1.2: 1.
8. The terbium ion doped upconversion nanomaterial according to claim 5, wherein:
the volume ratio of the oleic acid to the octadecene in the step (1) is 0.68: 1-0.82: 1;
the concentration of the holmium chloride solution in the step (1) is 0.85-1.15 mol.L-1；
The volume ratio of the oleic acid to the holmium chloride solution in the step (1) is 13: 1-17: 1;
in the methanol solution of sodium hydroxide and ammonium fluoride in the step (1), the concentration of sodium hydroxide is 0.23-0.27 mol/L;
in the methanol solution of sodium hydroxide and ammonium fluoride in the step (1), the concentration of ammonium fluoride is 0.39-0.41 mol/L;
the volume ratio of the holmium chloride solution to the methanol solution of sodium hydroxide and ammonium fluoride in the step (1) is 1: 8-1: 12;
the concentration of the terbium-oleic acid chelate in the step (2) and the step (3) is 0.038-0.042 mol.L-1；
The concentration of the yttrium-oleic acid chelate in the step (2) and the step (4) is 0.038-0.042 mol.L-1；
The volume ratio of the oleic acid to the yttrium-oleic acid chelate in the step (2) is 1: 0.06-1: 0.065;
in the methanol solution of sodium hydroxide and ammonium fluoride in the step (2), the step (3) and the step (4), the concentration of sodium hydroxide is 0.038-0.046 mol/L;
in the methanol solutions of sodium hydroxide and ammonium fluoride in the step (2), the step (3) and the step (4), the concentration of ammonium fluoride is 0.062-0.072 mol/L;
the volume ratio of the yttrium-oleic acid chelate to the methanol solution of sodium hydroxide and ammonium fluoride in the step (2) is 1: 9.2-1: 10;
the concentration of the ytterbium-oleic acid chelate in the step (3) is 0.038-0.042 mol.L-1；
The volume ratio of the methanol solution of sodium hydroxide and ammonium fluoride to the terbium-oleic acid chelate in the step (3) is 6: 1-10: 1;
the volume ratio of the methanol solution of sodium hydroxide and ammonium fluoride to the yttrium-oleic acid chelate in the step (4) is 2: 1-2.8: 1.
9. The terbium ion doped upconversion nanomaterial according to claim 5, wherein:
the temperature for heating to remove water in the step (1) is 98-112 ℃;
the temperature for removing the excessive methanol by heating in the step (1), the step (2), the step (3) and the step (4) is 88-92 ℃.
10. The terbium ion doped upconversion nanomaterial according to claim 5, wherein:
the volume ratio of oleic acid to octadecene in step (1) is 0.75: 1;
the concentration of the holmium chloride solution in the step (1) is 1 mol.L-1；
The volume ratio of the oleic acid to the holmium chloride solution in the step (1) is 15: 1;
the temperature for heating to remove water in the step (1) is 105 ℃;
the condition for generating the rare earth-oleic acid chelate by the high-temperature reaction in the step (1) is that the reaction is carried out for 40min at the temperature of 150 ℃;
in the methanol solution of sodium hydroxide and ammonium fluoride in the step (1), the concentration of sodium hydroxide is 0.25 mol/L;
in the methanol solution of sodium hydroxide and ammonium fluoride in the step (1), the concentration of ammonium fluoride is 0.4 mol/L;
the volume ratio of the holmium chloride solution to the methanol solution of sodium hydroxide and ammonium fluoride in the step (1) is 1: 10;
the concentration of the terbium-oleic acid chelate in the step (2) and the step (3) is 0.04 mol.L-1；
The concentration of the yttrium-oleic acid chelate in the step (2) and the step (4) is 0.04 mol.L-1；
The volume ratio of the oleic acid to the yttrium-oleic acid chelate in the step (2) is 1: 0.0625;
the nuclear layer NaHoF in the step (2)4The molar ratio of the nanoparticles to the yttrium-oleic acid chelate is 1: 0.25;
in the methanol solution of sodium hydroxide and ammonium fluoride in the step (2), the step (3) and the step (4), the concentration of sodium hydroxide is 0.042 mol/L;
in the methanol solutions of sodium hydroxide and ammonium fluoride in the step (2), the step (3) and the step (4), the concentration of ammonium fluoride is 0.067 mol/L;
the volume ratio of the yttrium-oleic acid chelate to the methanol solution of sodium hydroxide and ammonium fluoride in the step (2) is 1: 9.6;
ytterbium in the step (3)Concentration of-oleic acid chelate Compound 0.04 mol.L-1；
The terbium-oleic acid chelate in the step (3) and the nuclear layer NaHoF in the step (2)4The molar ratio of the nanoparticles is 0.3: 1;
the volume ratio of the methanol solution of sodium hydroxide and ammonium fluoride to the terbium-oleic acid chelate in the step (3) is 8: 1;
the yttrium-oleic acid chelate in the step (4) and the nuclear layer NaHoF in the step (2)4The molar ratio of the nanoparticles is 1: 1;
the volume ratio of the methanol solution of sodium hydroxide and ammonium fluoride to the yttrium-oleic acid chelate in the step (4) is 2.4: 1;
the temperature for removing the excessive methanol by heating in the step (1), the step (2), the step (3) and the step (4) is 90 ℃;
the high-temperature reaction conditions in the step (1), the step (2), the step (3) and the step (4) are reaction at 280 ℃ for 1 h.
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