CN108384544B - Tetragonal YPO4:Ln3+Spherical fluorescent particles and preparation method thereof - Google Patents

Tetragonal YPO4:Ln3+Spherical fluorescent particles and preparation method thereof Download PDF

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CN108384544B
CN108384544B CN201810018414.5A CN201810018414A CN108384544B CN 108384544 B CN108384544 B CN 108384544B CN 201810018414 A CN201810018414 A CN 201810018414A CN 108384544 B CN108384544 B CN 108384544B
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rare earth
ions
ypo
particles
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CN108384544A (en
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朱琦
许稚欣
李继光
李晓东
孙旭东
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • C09K11/7777—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7795—Phosphates

Abstract

The invention belongs to the field of material science, and relates to tetragonal YPO4: Ln3+ spherical fluorescent particles and a preparation method thereof. Step 1: dissolving cetyl trimethyl ammonium bromide in deionized water, adding urea, stirring to dissolve, adding yttrium nitrate solution and rare earth nitrate solution mixture,addition of H3PO4Adding deionized water to dilute the solution, and adding HNO3Adjusting the pH value to 0.5-1. Step 2: and stirring the clear and transparent solution at room temperature for 25-35 min. And step 3: heating to 80-100 deg.C, maintaining the temperature for 0-40min, naturally cooling the solution to room temperature, centrifuging, cleaning the reaction product, and placing the product in corundum crucible to obtain monodisperse spherical particle YPO4:Ln3+. The technical scheme of the invention is simple and easy to implement, and spherical particles with different sizes can be obtained by controlling the reaction temperature and the reaction time, so that the size can be controlled.

Description

Tetragonal YPO4:Ln3+Spherical fluorescent particles and preparation method thereof
Technical Field
The invention belongs to the field of material science, and particularly relates to tetragonal YPO4: Ln3+ spherical fluorescent particles and a preparation method thereof.
Background
Rare earth phosphate materials have recently gained much attention from researchers due to their advantages of strong absorption capacity, high conversion efficiency, stable physical and chemical properties, strong emission capacity in the ultraviolet-visible-infrared region, etc., and research using rare earth phosphates as a matrix has become a hotspot. At present, hydrothermal methods and sacrificial template methods are mostly used for researching preparation methods of rare earth phosphate systems, phosphor powder of phosphate matrixes obtained by the prior art is flaky, fusiform and other non-isometric particles, and scattering of incident light by the particles is large. Practical application shows that the spherical particles are ideal morphology of the fluorescent material. The spherical fluorescent particles with uniform size and good monodispersity are beneficial to improving the resolution of fluorescent components and parts, and a compact fluorescent layer is easy to form, so that the scattering of exciting light is reduced, and the optimal luminous efficiency is presented. However, direct synthesis and performance studies of spherical phosphate particles are currently reported.
The urea-based homogeneous precipitation technology (UBHP) is an effective way for preparing monodisperse phosphate spherical fluorescent particles, and a large amount of anions are generated in the slow decomposition process of urea at the temperature of not less than 83 ℃ after the temperature is raised, so that spherical powder particles with uniform size and good appearance are obtained. The microwave synthesis method is a new material preparation technology which is rapidly developed in recent years, and transmits microwaves emitted by a microwave reactor to a reactant system through an absorption medium, so that the reaction system is rapidly heated to the required temperature, and the reaction is completed in a short time. Microwave heating is different from the traditional heating method, which is body heating caused by dielectric loss in an electromagnetic field, the heat is generated from the inside of a material, the inside and the whole of components can be heated simultaneously, and the growth process of crystals can be influenced to a certain extent. In addition, the method has the advantages of simple and convenient operation, rapidness, high efficiency, time saving, energy saving, less environmental pollution, less side reaction, relatively simple product, contribution to realizing the automatic control of the heating process, improvement of working environment and working condition and the like.
Disclosure of Invention
The invention provides a tetragonal YPO4:Ln3+The spherical fluorescent particles and the preparation method thereof adopt a microwave method to research a rare earth phosphate system and successfully prepare the newly reported spherical fluorescent powder particles which take yttrium phosphate as a matrix and are doped with different rare earth ions, and the size of the obtained spherical fluorescent powder particles can be controlled by changing the reaction temperature and the reaction time.
The technical scheme of the invention is as follows:
tetragonal YPO4:Ln3+Spherical fluorescent particles, wherein the spherical fluorescent particles are tetragonal YPO with the size range of 0.7-1.5 mu m, and are prepared by taking rare earth nitrate as mother salt, urea as a precipitator, ethylene glycol as a mixed solvent and hexadecyl trimethyl ammonium bromide as a surfactant4:Ln3+Monodisperse spherical particles; wherein Ln is one of Ce, Pr, Eu, Tb, Dy, Ho, Tm, Tb + Eu and Gd + Dy.
The above tetragonal YPO4:Ln3+The preparation method of the spherical fluorescent particles comprises the following steps:
step 1: dissolving cetyl trimethyl ammonium bromide in deionized water, adding urea, stirring and dissolving, and adding a rare earth nitrate solution mixture, wherein the rare earth nitrate comprises yttrium nitrate and Ln nitrate; then adding H3PO4And a glycol solution, the solution being diluted with deionized water;
the diluted solution comprises the following components in concentration: rare earth ion concentration of 0.0075-0.03 mol/L, ethylene glycol concentration of 3.5-9 mol/L, H3PO4The concentration is 15-20 mol/L, and the molar concentration ratio of hexadecyl trimethyl ammonium bromide to rare earth ions is 1-4: 1; the molar concentration ratio of urea to rare earth ions is 5-200: 1;
adding HNO3Adjusting the pH value to 0.5-1.0;
step 2: stirring the clear and transparent solution at room temperature for 25-35 min, transferring the solution into a container, heating the solution in a microwave reactor at the heating temperature of 80-100 ℃, and keeping the temperature for 0-40 min;
and step 3: after the reaction is finished, naturally cooling the solution to room temperature, centrifugally separating, cleaning and drying the reaction product, and respectively calcining the reaction product in oxygen and hydrogen to obtain monodisperse spherical particle YPO4:Ln3+。
Further, in the step 1, the Ln nitrate is one of Ce, Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Tb + Eu and Gd + Dy nitrate.
When the rare earth nitrate is Y (NO)3)3、Tb(NO3)3And Eu (NO)3)3Wherein the molar ratio of the Y ions, the Tb ions and the Eu ions is 98-x:2: x, wherein x is more than or equal to 0.01 and less than or equal to 0.13.
When the rare earth nitrate is Y (NO)3)3、Gd(NO3)3And Dy (NO)3)3Wherein the molar ratio of the Y ions, the Gd ions and the Dy ions is 99-x: x:0.01, wherein x is more than or equal to 0.01 and less than or equal to 0.13.
When the rare earth nitrate is Y (NO)3)3、Tb(NO3)3And then, the molar ratio of the Y ion solution to the Tb ion solution is 100-x: x, wherein x is more than or equal to 1 and less than or equal to 5.
In the step 3, firstly, calcining in oxygen at the temperature of 600-1100 ℃ for 1.5-2.5 h; then calcining the mixture in hydrogen at the temperature of 600-1100 ℃ for 1.5-2.5 h.
And (3) drying at the temperature of 40-60 ℃.
The invention has the beneficial effects that:
according to the invention, a microwave method is firstly adopted to research a rare earth phosphate system, rare earth nitrate is used as mother salt, urea is used as a precipitator, Ethylene Glycol (EG) is used as a mixed solvent, and hexadecyl trimethyl ammonium bromide is used as a surfactant, so that tetragonal YPO with the size range of 0.7-1.5 mu m is successfully prepared4:Ln3+(Ln ═ Ce, Pr, Eu, Tb, Dy, Ho, Tm, Tb + Eu, Gd + Dy) monodisperse spherical particles. The technical scheme of the invention is simple and easy to implement, and spherical particles with different sizes can be obtained by controlling the reaction temperature and the reaction time, so that the size can be controlled.
Drawings
FIG. 1(a) is a YPO prepared in example 1 of the present invention4:Ln3+(Ln3+Ce) SEM topography of the particles.
FIG. 1(b) is a YPO prepared in example 1 of the present invention4:Ln3+(Ln3+Pr) SEM topography of the particles.
FIG. 1(c) is a YPO prepared in example 1 of the present invention4:Ln3+(Ln3+Nd) SEM topography of the particles.
FIG. 1(d) is a YPO prepared in example 1 of the present invention4:Ln3+(Ln3+Eu) SEM topography of the particles.
FIG. 1(e) is a YPO prepared in example 1 of the present invention4:Ln3+(Ln3+Tb) SEM topography of the particles.
FIG. 1(f) is a YPO prepared in example 1 of the present invention4:Ln3+(Ln3+Dy) SEM topography of the particles.
FIG. 1(g) is a YPO prepared in example 1 of the present invention4:Ln3+(Ln3+Ho) SEM topography of the particles.
FIG. 1(h) is thisYPO prepared in inventive example 14:Ln3+(Ln3+Er) particles.
FIG. 1(i) is a YPO prepared in example 1 of the present invention4:Ln3+(Ln3+Tm) SEM topography of the particles.
Figure 2 is an XRD pattern of the product prepared in example 1 of the present invention.
FIG. 3(a) is (Y) prepared in example 2 of the present invention0.98-xTb0.02Eux)PO4(0.01 is less than or equal to x is less than or equal to 0.13), and x is 0.01 of the SEM topography of the particles.
FIG. 3(b) is (Y) prepared in example 2 of the present invention0.98-xTb0.02Eux)PO4(x is more than or equal to 0.01 and less than or equal to 0.13), and x is 0.02 of the SEM topography of the particles.
FIG. 3(c) is (Y) prepared in example 2 of the present invention0.98-xTb0.02Eux)PO4(0.01 is less than or equal to x is less than or equal to 0.13), and x is 0.03.
FIG. 3(d) is (Y) prepared in example 2 of the present invention0.98-xTb0.02Eux)PO4(x is more than or equal to 0.01 and less than or equal to 0.13), and x is 0.04 of the SEM topography of the particles.
FIG. 3(e) is (Y) prepared in example 2 of the present invention0.98-xTb0.02Eux)PO4(0.01 is less than or equal to x is less than or equal to 0.13), and x is 0.05.
FIG. 3(f) is (Y) prepared in example 2 of the present invention0.98-xTb0.02Eux)PO4(0.01 ≦ x ≦ 0.13), and x ≦ 0.08 SEM topography of the particles.
FIG. 3(g) is (Y) prepared in example 2 of the present invention0.98-xTb0.02Eux)PO4(x is more than or equal to 0.01 and less than or equal to 0.13), and x is 0.010 particles.
FIG. 3(h) is (Y) prepared in example 2 of the present invention0.98-xTb0.02Eux)PO4(0.01 ≦ x ≦ 0.13), and x ≦ 0.013 particles.
Figure 4 is an XRD pattern of the product prepared in example 2 of the present invention.
FIG. 5(a) is (Y) prepared in example 3 of the present invention0.99-xGdxDy0.01)PO4(x is more than or equal to 0.03 and less than or equal to 0.2), x is 0.03, and an SEM topography of particles.
FIG. 5(b) is (Y) prepared in example 3 of the present invention0.99-xGdxDy0.01)PO4(x is more than or equal to 0.03 and less than or equal to 0.2), and x is 0.05.
FIG. 5(c) is (Y) prepared in example 3 of the present invention0.99-xGdxDy0.01)PO4(x is more than or equal to 0.03 and less than or equal to 0.2), and x is 0.10 of the SEM topography of the particles.
FIG. 5(d) is (Y) prepared in example 3 of the present invention0.99-xGdxDy0.01)PO4(x is more than or equal to 0.03 and less than or equal to 0.2), and x is 0.15.
FIG. 5(e) is (Y) prepared in example 3 of the present invention0.99-xGdxDy0.01)PO4(0.03 is less than or equal to x is less than or equal to 0.2), and x is 0.20 of the SEM topography of the particles.
Figure 6 is an XRD pattern of the product prepared in example 3 of the present invention.
FIG. 7(a) shows different reaction times (Y) for the preparation of example 4 of the present invention0.98Tb0.02)PO4And T is SEM topography of 1min particles.
FIG. 7(b) is a graph of the different reaction times (Y) for the preparation of example 4 of the present invention0.98Tb0.02)PO4And T is an SEM topography of 3min particles.
FIG. 7(c) is a graph of the different reaction times (Y) for the preparation of example 4 of the present invention0.98Tb0.02)PO4And T is an SEM topography of 5min particles.
FIG. 7(d) is a graph of the different reaction times (Y) for the preparation of example 4 of the present invention0.98Tb0.02)PO4And T is SEM topography of 10min particles.
FIG. 7(e) is a graph of the different reaction times (Y) for the preparation of example 4 of the present invention0.98Tb0.02)PO4And T is an SEM topography of 20min particles.
FIG. 7(f) is a graph of the different reaction times (Y) for the preparation of example 4 of the present invention0.98Tb0.02)PO4And T is the SEM topography of the 40min particles.
Figure 8 is an XRD pattern of the product prepared in example 4 of the present invention.
FIG. 9(a) shows different reaction temperatures (Y) for the preparation of example 5 of the present invention0.98Tb0.02)PO4SEM topography of particles at 80 ℃.
FIG. 9(b) is a graph showing different reaction temperatures (Y) for the preparation of example 5 of the present invention0.98Tb0.02)PO4And the temperature is 90 ℃ and the SEM topography of the particles is shown.
FIG. 9(c) is a graph of different reaction temperatures (Y) for the preparation of example 5 of the present invention0.98Tb0.02)PO4And the temperature is 100 ℃ and the SEM topography of the particles is shown.
FIG. 10(a) is CTAB prepared in example 6 of the present invention: rare earth element ion 1: 1 time (Y)0.98Tb0.02)PO4SEM topography of the particles.
FIG. 10(b) is CTAB prepared in example 6 of the present invention: rare earth element ion 2: 1 time (Y)0.98Tb0.02)PO4SEM topography of the particles.
FIG. 10(c) is CTAB prepared in example 6 of the present invention: rare earth element ion 4:1 time (Y)0.98Tb0.02)PO4SEM topography of the particles.
FIG. 11(a) is an SEM morphology of (Y0.95Eu0.05) PO4 particles at total mole of 0.00375 moles of rare earth element ions prepared in example 7 of the present invention.
FIG. 11(b) is an SEM photograph of particles of PO4 (Y0.95Eu0.05) when the total molar amount of the rare earth element ions prepared in example 7 of the present invention is 0.0075 mol.
FIG. 11(c) is a graph showing that when the total molar number of the rare earth element ions prepared in example 7 of the present invention is 0.015mol (Y)0.95Eu0.05)PO4SEM topography of the particles.
Figure 12 is an XRD pattern of the products prepared in examples 5-7 of the present invention.
FIG. 13(a) is a graph showing that the ethylene glycol solution prepared in example 8 of the present invention has a content of 125mL (Y)0.95Eu0.05)PO4SEM topography of the particles.
FIG. 13(b) is a graph showing the results of a 150 mL-content ethylene glycol solution prepared in example 8 of the present invention (Y)0.95Eu0.05)PO4SEM topography of the particles.
FIG. 13(c) is a graph showing that the ethylene glycol solution prepared in example 8 of the present invention has a content of 200mL (Y)0.95Eu0.05)PO4SEM topography of the particles.
FIG. 13(d) is a graph showing the results of the experiment of the present invention in which the ethylene glycol solution prepared in example 8 had a content of 250mL (Y)0.95Eu0.05)PO4SEM topography of the particles.
Figure 14 is an XRD pattern of the product prepared in example 8 of the invention.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
The chemical reagents adopted in the embodiment of the invention are all analytical pure-grade products;
example 1
Dissolving cetyl trimethyl ammonium bromide in 100ml deionized water, adding urea, stirring to dissolve, adding Y (NO)3)3The solution is separately mixed with Ce (NO)3)3、Pr(NO3)3、Nd(NO3)3、Eu(NO3)3、Tb(NO3)3、 Dy(NO3)3、Ho(NO3)3、Er(NO3)3、Tm(NO3)3The solution is a mixture mixed according to a molar ratio Y/Ln of 99:1, and the addition amount of CTAB is the molar ratio of CTAB: rare earth element ion 2: 1, adding the urea in a molar ratio of urea: 33.333, the total molar amount of rare earth element ions is 0.0075 mol. 15mL of H was added3PO4Adding 125mL of glycol solution, adding deionized water to prepare 500mL of the solution, and adding a proper amount of HNO3The pH was adjusted to 1.0.
Stirring the clear and transparent solution at normal temperature for 30min, transferring the solution into a three-neck flask, heating to 100 ℃ in a microwave reactor, and keeping the temperature for 20 min.
After the reaction is finished, taking out the three-neck flask, naturally cooling to room temperature, centrifugally separating and cleaning a reaction product, drying at 40 ℃, placing the product in a corundum crucible at 600 DEG CCalcining in oxygen and 600 deg.C hydrogen for 1.5 hr to obtain monodisperse spherical particle YPO4:Ln3+(Ce、Pr、Nd、Eu、Tb、Dy、Ho、Er、 Tm)。
The obtained spherical particles have a size of about 1 μm and good dispersibility, as shown in FIG. 1(a) (Y)0.99Ce0.01)PO4FIG. 1(b) (Y)0.99Pr0.01)PO4FIG. 1(c) (Y)0.99Nd0.01)PO4FIG. 1(d) (Y)0.99Eu0.01)PO4FIG. 1(e) (Y)0.99Tb0.01)PO4FIG. 1(f) (Y)0.99Dy0.01)PO4FIG. 1(g) (Y)0.99Ho0.01)PO4FIG. 1(h) (Y)0.99Er0.01)PO4FIG. 1(i) (Y)0.99Tm0.01)PO4。
The XRD pattern is shown in FIG. 2, from which it can be seen that a phosphate pure phase is obtained.
Example 2
Dissolving Cetyl Trimethyl Ammonium Bromide (CTAB) in 100ml deionized water, adding urea, stirring to dissolve, adding Y (NO)3)3Solution with Tb (NO)3)3、Eu(NO3)3The solution is a mixture mixed according to a molar ratio of Y/Tb/Eu, 98-x:2: x (0.01 ≤ x ≤ 0.13), and the addition amount of CTAB is as follows according to the molar ratio of CTAB: rare earth element ion 2: 1, adding the urea in a molar ratio of urea: the total molar amount of the rare earth element ions is 0.0075 mol. 15mL of H was added3PO4Adding 125mL of glycol solution, adding deionized water to prepare 500mL of the solution, and adding a proper amount of HNO3The pH was adjusted to 0.75.
Stirring the clear and transparent solution at normal temperature for 25min, transferring the solution into a three-neck flask, heating to 90 ℃ in a microwave reactor, and keeping the temperature for 20 min.
After the reaction is finished, taking out the three-neck flask, naturally cooling to room temperature, centrifugally separating and cleaning a reaction product, drying at 45 ℃, putting the product into a corundum crucible, and respectively calcining in oxygen at 1000 ℃ and hydrogen at 1000 ℃ for 2 hours to obtain monodisperse spherical particles (Y0.98-xTb0.02Eux)PO4(0.01≤x≤0.13)。
The obtained spherical particles had a size of about 1 μm and good dispersibility, as shown in FIG. 3(a) (Y)0.97Tb0.02Eu0.01)PO4FIG. 3(b) (Y)0.96Tb0.02Eu0.02)PO4FIG. 3(c) (Y)0.95Tb0.02Eu0.03)PO4FIG. 3(d) (Y)0.94Tb0.02Eu0.04)PO4FIG. 3(e) (Y)0.93Tb0.02Eu0.05)PO4FIG. 3(f) (Y)0.90Tb0.02Eu0.08)PO4FIG. 3(g) (Y)0.88Tb0.02Eu0.10)PO4FIG. 3(h) (Y)0.85Tb0.02Eu0.13)PO4。
The XRD pattern is shown in FIG. 4, from which it can be seen that a phosphate pure phase is obtained.
Example 3
Dissolving cetyl trimethyl ammonium bromide in 100ml deionized water, adding urea, stirring to dissolve, adding Y (NO)3)3Solution with Gd (NO)3)3、Dy(NO3)3The solution is a mixture mixed according to the molar ratio of Y/Gd/Dy which is 99-x: x:0.01 (x is more than or equal to 0.01 and less than or equal to 0.13), and the addition amount of CTAB is that the molar ratio of CTAB: rare earth element ion 2: 1, adding the urea in a molar ratio of urea: the total molar amount of the rare earth element ions is 50, and the total molar amount of the rare earth element ions is 0.0075 mol. 15mL of H was added3PO4Adding 125mL of glycol solution, adding deionized water to prepare 500mL of the solution, and adding a proper amount of HNO3The pH was adjusted to 0.7.
Stirring the clear and transparent solution at normal temperature for 35min, transferring the solution into a three-neck flask, placing the three-neck flask in a microwave reactor, heating to 80 ℃, and preserving heat for 5 min.
After the reaction is finished, taking out the three-neck flask, naturally cooling to room temperature, centrifugally separating and cleaning a reaction product, drying at 50 ℃, putting the product into a corundum crucible, and calcining at 1100 ℃ for 2.5 hours by using oxygen to obtain monodisperse spherical particles (Y)0.99- xGdxDy0.01)PO4(0.03≤x≤0.2)。
The obtained spherical particles had a size of about 1 μm and good dispersibility, as shown in FIG. 5(a) (Y)0.96Gd0.03Dy0.01)PO4FIG. 5(b) (Y)0.94Gd0.05Dy0.01)PO4FIG. 5(c) (Y)0.89Gd0.10Dy0.01)PO4FIG. 5(d) (Y)0.84Gd0.15Dy0.01)PO4FIG. 5(e) (Y)0.79Gd0.20Dy0.01)PO4。
The XRD pattern is shown in FIG. 6, from which it can be seen that a phosphate pure phase is obtained.
Example 4
Dissolving Cetyl Trimethyl Ammonium Bromide (CTAB) in 100ml deionized water, adding urea, stirring to dissolve, adding Y (NO)3)3Solution with Tb (NO)3)3The solution is a mixture mixed according to a molar ratio Y/Tb 98:2, and the addition amount of CTAB is the molar ratio of CTAB: rare earth element ion 2: 1, adding the urea in a molar ratio of urea: the total molar amount of the rare earth element ions is 80, and the molar amount of the rare earth element ions is 0.0075 mol. 15mL of H was added3PO4Adding 125mL of glycol solution, adding deionized water to prepare 500mL of the solution, and adding a proper amount of HNO3The pH was adjusted to 0.65.
Stirring the clear and transparent solution at room temperature for 30min, transferring the solution into a three-neck flask, heating to 85 deg.C in a microwave reactor, and collecting the reaction solution at 1min, 3min, 5min, 10min, 20min, and 40 min.
Naturally cooling the reaction solution to room temperature, centrifugally separating and cleaning the reaction product, and drying at 55 ℃ to obtain monodisperse spherical particles (Y) under different reaction times0.98Tb0.02)PO4。
The obtained spherical particles have a size of 450nm-1.5 μm and good dispersibility, such as 1min in FIG. 7(a), 3min in FIG. 7(b), 5min in FIG. 7(c), 10min in FIG. 7(d), 20min in FIG. 7(e), and 40min in FIG. 7 (f).
The XRD pattern is shown in FIG. 8, from which it can be seen that all the phases obtained in different stages of the reaction are phosphate pure phases.
Example 5
Dissolving Cetyl Trimethyl Ammonium Bromide (CTAB) in 100ml deionized water, adding urea, stirring to dissolve, adding Y (NO)3)3Solution with Tb (NO)3)3The solution is a mixture mixed according to a molar ratio Y/Tb 98:2, and the addition amount of CTAB is respectively as follows according to the molar ratio CTAB: rare earth element ion 2: 1, adding the urea in a molar ratio of urea: the total molar amount of the rare earth element ions is 0.0075 mol. 15mL of H was added3PO4Adding 125mL of glycol solution, adding deionized water to prepare 500mL of the solution, and adding a proper amount of HNO3The pH was adjusted to 0.6.
Stirring the clear and transparent solution at room temperature for 30min, transferring the solution into a three-neck flask, placing in a microwave reactor, heating to 80 deg.C, 90 deg.C, 100 deg.C, and maintaining the temperature for 10 min.
Naturally cooling the reaction solution to room temperature, centrifugally separating and cleaning the reaction product, and drying at 60 ℃ to obtain monodisperse spherical particles (Y) at different reaction temperatures0.98Tb0.02)PO4。
The obtained spherical particles have a size of about 1 μm and good dispersibility, as shown in FIG. 9(a)80 deg.C, FIG. 9(b)90 deg.C, and FIG. 9(c)100 deg.C.
The XRD patterns are shown in figure 12(a), figure 12(b) and figure 12(c), and the figures show that the phases are all phosphate pure phases.
Example 6
Cetyl trimethylammonium bromide (CTAB) was dissolved in 100ml of deionized water, and the CTAB was added in the molar ratio CTAB: rare earth element ion 1: 1. 2: 1. 4:1, adding urea, stirring to dissolve, adding Y (NO)3)3Solution with Tb (NO)3)3The solution is mixed according to a molar ratio Y/Tb of 98:2, and the adding amount of the urea is that the molar ratio of urea: the total molar amount of the rare earth element ions is 120, and the total molar amount of the rare earth element ions is 0.0075 mol. 15mL of H was added3PO4And 125mL of ethylene glycol solution, adding deionized water to prepare 500mL of the solutionAdding appropriate amount of HNO3The pH was adjusted to 0.5.
Stirring the clear and transparent solution at normal temperature for 30min, transferring the solution into a three-neck flask, placing the three-neck flask in a microwave reactor, heating to 90 ℃, and preserving heat for 20 min.
Naturally cooling the reaction solution to room temperature, centrifugally separating and cleaning the reaction product, and drying at 50 ℃ to obtain monodisperse spherical particles (Y) under different reaction times0.98Tb0.02)PO4。
The obtained spherical particles have a size of about 1 μm and good dispersibility, as shown in FIG. 10(a) CTAB: rare earth element ion 1: 1, FIG. 10(b) CTAB: rare earth element ion 2: 1, FIG. 10(c) CTAB: rare earth element ion 4: 1.
the XRD patterns are shown in figure 12(d), figure 12(e) and figure 12(f), and the figures show that the phases are all phosphate pure phases.
Example 7
Cetyl trimethylammonium bromide (CTAB) was dissolved in 100ml of deionized water, and the CTAB was added in the molar ratio CTAB: rare earth element ion 1: 1. 2: 1. 4:1, adding urea, stirring to dissolve, adding Y (NO)3)3Solution with Tb (NO)3)3Solution mixed according to molar ratio Y/Eu 95:5, the addition of urea is according to the molar ratio urea: the total molar amount of the rare earth element ions is 0.00375mol, 0.0075mol and 0.015mol, respectively. 15mL of H was added3PO4Adding 125mL of glycol solution, adding deionized water to prepare 500mL of the solution, and adding a proper amount of HNO3The pH was adjusted to 0.85.
Stirring the clear and transparent solution at normal temperature for 30min, transferring the solution into a three-neck flask, heating to 95 ℃ in a microwave reactor, and keeping the temperature for 30 min.
Naturally cooling the reaction solution to room temperature, centrifugally separating and cleaning the reaction product, and drying at 50 ℃ to obtain monodisperse spherical particles (Y) under different reaction times0.98Tb0.02)PO4。
The obtained spherical particles had a size of about 1 μm and good dispersibility, as shown in FIG. 11, in which 0.00375mol in FIG. 12(a), 0.0075mol in FIG. 12(b) and 0.015mol in FIG. 12 (c).
The XRD patterns are shown in figure 12(g), figure 12(h) and figure 12(i), and the figures show that the phases are all phosphate pure phases.
Example 8
Cetyl trimethylammonium bromide (CTAB) was dissolved in 100ml of deionized water, and the CTAB was added in the molar ratio CTAB: rare earth element ion 2: 1, adding urea, stirring to dissolve, adding Y (NO)3)3Solution with Tb (NO)3)3Solution mixed according to molar ratio Y/Eu 95:5, the addition of urea is according to the molar ratio urea: the total molar amount of the rare earth element ions is 200, and the total molar amount of the rare earth element ions is 0.0075 mol. 15mL of H was added3PO4Adding 125mL, 150mL, 200mL and 250mL of glycol solution respectively, adding deionized water to prepare 500mL of the solution, and adding a proper amount of HNO3The pH was adjusted to 0.9.
Stirring the clear and transparent solution at normal temperature for 30min, transferring the solution into a three-neck flask, heating to 100 ℃ in a microwave reactor, and keeping the temperature for 40 min.
Naturally cooling the reaction solution to room temperature, centrifugally separating and cleaning the reaction product, and drying at 50 ℃ to obtain monodisperse spherical particles (Y) under different reaction times0.98Tb0.02)PO4。
The obtained spherical particles have a size of 500nm-1 μm and good dispersibility, as shown in FIG. 13(a), FIG. 13(b), FIG. 13(c) and FIG. 13 (d).
The XRD patterns are shown in FIG. 14, from which it can be seen that they are all phosphate pure phases.

Claims (7)

1. Tetragonal YPO4:Ln3+The preparation method of the spherical fluorescent particles is characterized in that the spherical fluorescent particles are prepared by taking rare earth nitrate as mother salt, urea as precipitator, ethylene glycol as mixed solvent and hexadecyl trimethyl ammonium bromide as surfactant to obtain tetragonal YPO with the size range of 0.7-1.5 mu m4:Ln3+Monodisperse spherical particles; wherein Ln is CePr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Tb + Eu and Gd + Dy;
the preparation method comprises the following steps:
step 1: dissolving cetyl trimethyl ammonium bromide in deionized water, adding urea, stirring and dissolving, and adding a rare earth nitrate solution mixture, wherein the rare earth nitrate comprises yttrium nitrate and Ln nitrate; then adding H3PO4And a glycol solution, the solution being diluted with deionized water;
the diluted solution comprises the following components in concentration: the concentration of rare earth ions is 0.0075-0.03 mol/L, the concentration of ethylene glycol is 3.5-9 mol/L, H3PO4The concentration is 15-20 mol/L, and the molar concentration ratio of hexadecyl trimethyl ammonium bromide to rare earth ions is 1-4: 1; the molar concentration ratio of urea to rare earth ions is 5-200: 1;
adding HNO3Adjusting the pH value to 0.5-1.0;
step 2: stirring the clear and transparent solution obtained in the step 1 at room temperature for 25-35 min, transferring the solution into a container, heating the solution in a microwave reactor at the heating temperature of 80-100 ℃, and keeping the temperature for 0-40 min;
and step 3: after the reaction is finished, naturally cooling the solution to room temperature, centrifugally separating, cleaning and drying the reaction product, and respectively calcining the reaction product in oxygen and hydrogen to obtain monodisperse spherical particle YPO4:Ln3+。
2. The tetragonal YPO according to claim 14:Ln3+The preparation method of the spherical fluorescent particles is characterized in that in the step 1, when the rare earth nitrate is Y (NO)3)3、Tb(NO3)3And Eu (NO)3)3And the molar ratio of the Y ions, the Tb ions and the Eu ions is 98-x:2: x, wherein x is more than or equal to 1 and less than or equal to 13.
3. The tetragonal YPO according to claim 14:Ln3+The preparation method of the spherical fluorescent particles is characterized in that in the step 1, when the rare earth nitrate is Y (NO)3)3、Gd(NO3)3And Dy (NO)3)3Wherein the molar ratio of the Y ions to the Gd ions to the Dy ions is 99-x: x:1, wherein x is more than or equal to 1 and less than or equal to 13.
4. The tetragonal YPO according to claim 14:Ln3+The preparation method of the spherical fluorescent particles is characterized in that in the step 1, when the rare earth nitrate is Y (NO)3)3、Tb(NO3)3Wherein the molar ratio of the Y ions to the Tb ions is 100-x: x, wherein x is more than or equal to 1 and less than or equal to 5.
5. The tetragonal YPO according to any one of claims 1 to 44:Ln3+The preparation method of the spherical fluorescent particles is characterized in that in the step 3, the spherical fluorescent particles are firstly calcined in oxygen at the temperature of 600-1100 ℃ for 1.5-2.5 h; and then calcining in hydrogen at 600-1100 ℃ for 1.5-2.5 h.
6. The tetragonal YPO according to any one of claims 1 to 44:Ln3+The preparation method of the spherical fluorescent particles is characterized in that the drying temperature in the step 3 is 40-60 ℃.
7. The tetragonal YPO according to claim 54:Ln3+The preparation method of the spherical fluorescent particles is characterized in that the drying temperature in the step 3 is 40-60 ℃.
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